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Not even looking at how much of a ball ache trying to sort out which trains and what stupid requirements they have, it's the price/time that kills it. It's why I fly most of the time. At least they're pretty consistently shit and I know how to work around it. Trains w/ bikes seem so random. The same journey you've taken one time - you take again but get a different train or different conductor and you're fucked.
Yeah but connections are a bit shit here... sleeper tickets seem to be released at random intervals which is not ideal if you're planning for an event. I can't get one of those I have to get a hotel in Barcelona, Valence or Paris for a night and still have about 18 hours on a train. I do like the idea of traveling by train tho...
Edit - Looks like there is one way to do it with a sleeper but it's still an arse ache. 3pm leave Luxembourg on TGV (so bike in a bag) for Paris, put wheels on and ride across Paris. 8pm sleeper from Paris to Montpellier (back in bag). 9:30am train to Tarragona. 6 hour wait there, then final train to Valencia arriving 9pm.
So total: 19 hours on trains, 10 hours either waiting in stations or going between them. Or a 2 hour flight. Only advantage of the train is I know where my bike is most of the time.