I recently delved into the booking process for Thello trains for Paris-Milan, and I discovered some interesting (and frustrating) things that others will probably find useful.
Searching on Loco2
My journey was starting in London and going all the way through to Milan and back, so I started off by searching for London-Milan return on Loco2.
I got reasonable times and prices in my search results, so I proceeded through the booking process, only to be told when proceeding to payment that it wasn't possible to book the train (this is a problem in the SNCF booking system Loco2 is integrated with).
Identifying which leg I couldn't book
It wasn't clear from the message why the train wasn't available, and checking the search logs on the back-end didn't shed much light either (although we did determine that it had something to do with the Hermes booking system, which is accessed by the SNCF booking system). So I had to do some manual research, splitting the outbound journey into London-Paris, Paris-Milan.
The London-Paris Eurostar leg was fine (as usual), and when I searched for Paris-Milan and tried to proceed to booking, it became clear that the issue was with that leg. I knew that this was a Thello train (the name of the night-train service that runs from Paris to Milan and Venice), and so because it wasn't available to book on Loco2, I headed over to the Thello website to see if I could book it directly.
Booking on the Thello site
The Thello site is only available in French, so it was slightly tricky to find the trains and book, and I had to use Google Translate to clarify certain things, but generally it was straightforward and I managed to find the same train times that were in the Loco2 search results. The prices were slightly cheaper than the ones that I saw on Loco2, but wasn't able to book.
One thing that was a bit worrying on the Thello site was that I was never asked for a postal address. This is because Thello only offers a 'ticketless' journey - you just take a code from your booking confirmation email and quote that to the conductor, similar to print-at-home tickets.
Another thing that was really annoying was the lack of "UK", "Great Britain" or anything like it in the drop-down menu for 'country of residence'. Eventually I worked out that I needed to select Royaume-Uni.
Once I'd overcome these hurdles and received my confirmation email I was confident that everything was fine and that I would be able to travel successfully.
Conclusion and tips
I concluded that the reason that the tickets showed up on Loco2 but then weren't available to book, is because Rail Europe has a certain number of Thello tickets allocated (at a slightly more expensive price) from the Thello booking system, but no access to remaining tickets after this initial allocation is sold out. For some reason these tickets/price aren't removed fully even when they are sold out and that's why they show up in the search results but aren't available for booking. This is annoying (for me and other Loco2 customers) but unfortunately there is nothing we can do about it at this stage as it is in the hands of Rail Europe and Thello.
If trying to book a similar journey, I would recommend following these tips:
Try searching for the whole journey on Loco2, preferably a full three months in advance. The earlier you search, the more likely it is that you'll be able to book the entire journey at a reasonable price, and in one transaction
If the trains become unavailable when you try and proceed to purchase it's probably due to the Paris-Milan/Venice not actually being available. You can double-check by splitting the journey and searching just for Paris-Milan/Venice. Unfortunately this means that you'll have to make two purchases (you can still book the London-Paris part on Loco2).
Search at Thello for the same trains that you see in the Loco2 results and book them there
Note that you can also try booking at TrenItalia instead of Thello, but a quick check shows that although the site is available in English, it's not as easy to choose different sleeper compartments, and the prices seem more expensive then directly on Thello.
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