A Rome-Florence-Venice itinerary 14 days (un itinerario di 14 giorni tra Roma, Firenze, e Venezia) is the gold standard of Italian first-time visits: enough days to actually breathe in each city, enough day trips to understand the surrounding region, and enough Italian meals to start developing the specific food vocabulary (the difference between the specific Roman carbonara (no cream, no peas, no pancetta, only guanciale, egg, and pecorino), the specific Florentine bistecca (only from the specific Chianina breed, aged minimum 15 days, served blue-rare on the bone at minimum 700g), and the specific Venetian cicchetti (the canalside bar snacks at €1-2 each, the Venetian equivalent of tapas) requires the time to try them all properly, which the 14-day program provides).
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Rome Florence Venice 14-Day Itinerary: The Full Program

Days 1-5: Rome (with Tivoli and Pompeii)
Days 1-3: see the How Many Days in Rome guide 3-night program. Day 4 (Tivoli): see the Rome-Florence-Venice 10-Day Itinerary Day 4 Tivoli program. Day 5 (Pompeii day trip from Rome): the Frecciarossa Roma Termini → Napoli Centrale (1h10m, €30-45) + the Circumvesuviana Napoli Garibaldi → Pompei Scavi (38 minutes, €3) → Pompeii full day (see the How Many Days in Naples guide Day 3 for the full Pompeii program) → return to Rome via the same route (evening). The 14-day program Rome addition: the Ostia Antica (see the Italy for History Nerds guide) as an alternative to Tivoli on Day 4 for the visitor who prefers the Roman archaeology to the Renaissance garden. The Rome-Florence 14-day train: pre-book the Frecciarossa Roma Termini → Firenze SMN for the Day 5 evening (after returning from Pompeii) or Day 6 morning (the most specifically restful single transfer: Day 6 morning departure gives the Day 5 afternoon in Rome for the Campo de' Fiori aperitivo (pre-dinner drink with snacks) goodbye).
Days 6-9: Florence (with Siena and Chianti)
Day 6 Florence (Uffizi): see the Rome-Florence-Venice 10-Day Itinerary Day 5. Day 7 Florence (Duomo and Accademia): see Day 6 of the same program. Day 8 (Siena day trip): the Trenitalia Regionale from Firenze SMN to Siena (1h30m, approximately €9.30), the most specifically rewarding single Florence day trip (see the Tuscany 5-Day Itinerary Day 4 for the Siena program). Day 9 (Chianti wine road): rental car day trip from Florence (see the Tuscany 5-Day Itinerary Day 3 for the Chianti program). The 14-day Florence addition: the Boboli Gardens (GPS: 43.7638°N, 11.2494°E, the most specifically extensive single Florentine royal garden (the Medici Grand Duchy's 4.5-hectare garden behind the Palazzo Pitti): admission €10, the most specifically "Medici outdoor life" single Florence experience, the Isolotto pond, the Ammanati grotto, and the amphitheater are the 3 most specifically spectacular single Boboli garden elements). Florence → Venice: Frecciarossa Firenze SMN → Venezia Santa Lucia (2h20m, €35-50 advance).
Days 10-14: Venice (with Verona and Padova)
Days 10-11: see the Rome-Florence-Venice 10-Day Itinerary Days 8-9 for the Venice San Marco, Dorsoduro, and Cannaregio programs. Day 12 (Verona): see the Rome-Florence-Venice 10-Day Itinerary Day 10 Verona program. Day 13 (Padova day trip): the Trenitalia Regionale from Venezia Santa Lucia to Padova (30 minutes, approximately €4.50): the Cappella degli Scrovegni (GPS: 45.4076°N, 11.8730°E, the most specifically important single room in Western art (the Giotto 1304-1306 fresco cycle of the Life of the Virgin and the Life of Christ: the 37-scene program that establishes every principle of pictorial space, emotional naturalism, and narrative psychology that defines the next 700 years of Western painting)): timed entry required, book at cappelladegliscrovegni.it at least 2 weeks in advance (€8, maximum 25 persons per 15-minute slot, the most strictly limited single Italian art monument after the Borghese Gallery). The Basilica di Sant'Antonio (GPS: 45.4013°N, 11.8815°E, the most important single Catholic pilgrimage site in northern Italy: the saint's tomb and the specific Donatello equestrian statue (the Gattamelata. GPS: 45.4013°N, 11.8817°E, the 1453 bronze equestrian statue of the condottiere Erasmo da Narni: the first single large-scale freestanding bronze equestrian statue cast in Europe since Roman antiquity): free. Day 14 (final Venice morning and departure): the Murano glass island (the No. 4.1 vaporetto (Venice water bus) from Fondamenta Nuove: 20 minutes + the standard Venezia Unica transport ticket) with the glass-blowing demonstration (free at most Murano fornaci (kilns)) and the optional glass buy. Departure from Venice Marco Polo airport (ATVO bus from Piazzale Roma: 25 minutes, €8).

Q&A: Rome Florence Venice 14-Day Itinerary
What is the best 14-day Italy structure if I've already done Rome-Florence-Venice once?
The specific "second Italy trip" 14-day structure: Naples (3 days) + Amalfi Coast (3 days) + Sicily (4 days: Palermo, Agrigento, Siracusa, Taormina) + Puglia (4 days: Lecce, Alberobello, Bari), the most specifically geographic and culturally opposite program to the Rome-Florence-Venice circuit, covering the most specifically Italian-Italy that the international visitor never sees on the first trip. This program uses Catania as the departure point (the Ryanair and Vueling Catania flights to European cities are the most affordable single southern Italy exit) after the Puglia segment (Bari → ferry to Bar, Montenegro → or direct flight Bari to home).