Flying to Venice (Italy) and driving a rental car to Buje (Croatia)

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it would require crossing from Italy to Slovenia and the from Solvenia into Croatia

All of those states are part of the Schengen Area, you are free to cross Italy -> Slovenia -> Croatia, without any border control or formalities. As you'll achieve those formalities on arrival at Venice.

is travelling this route by car advisable?

Outside of the acclimatation to right hand driving, it's only motorways and I don't see any major roadblocks to this

What you must make sure is that the rental car company allows you to go into Croatia and Slovenia

Upvote:5

If you are planning a one-way rental (it's not clear from your question), in my recent experience (April 2023) I could not find any car hire firm prepared to offer a one-way from Italy to any of Austria, Slovenia, Croatia. No idea why. Hertz Slovenia were happy to offer one-way to Austria or Slovenia.

The actual border crossings will be embarrassingly easy, compared (say) to the rigmarole to be found at any UK border... Indeed, once (accidentally) I drove Slovenia - Italy - Austria and back again without actually having my passport with me at all - but it was fine because no one cared to check.

edit I forgot to mention, although you may well already be aware, that use of highways (motorways) in Slovenia requires an e-vignette, essentially an electronic toll pass. You can buy this online once you know your hire car's registration number. Italy and Croatia have no such payment required.

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