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Cheers, it's showing as possible now I just stop at the border. I'll have to see a bit closer to the time for tickets etc as currently SNCF only does night train availability 2-4 months before departure. I've seen photos of bikes on the night train but I've got one of those TGV compatible bike covers I could use if needed just to get the bike on the train.
All that said, to get to Valencia it's looking like 30 hours more or less. Plane considerably less.
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I'd have to add, I found it incredibly difficult to get to sleep on the train. I think if I were doing it again, I'd get the train from Paris to somewhere like Montpellier or Narbonne and stay overnight in a hotel, then get the train down to Barcelona. And in your case, on to Valencia. While in theory you save on the hotel going by night train, in practice you barely get any real rest and certainly not the kind you'd want before a cycling event.
ketsbaia
I've done the Paris-Latour de Carol/Enveitg and then onto Barcelona a couple of times. You book the Paris-Latour de Carol leg first, then wait for the regional train (Rodalies) to Barcelona, which is a scenic route that takes around three hours. You can't book the latter, which is probably why SNCF won't route you to Barcelona that way.
Not sure you can take a bike on the night train, though. But if you can, the Rodalies train should have space for you to take it on board, especially since you'll be one of the first to board the train.