Vueling is a low-cost airline http://en.wikipedia.org/wiki/Vueling . This means that the cheap price you are seeing may not include fees for baggage or other optional services (meals, drinks, etc.). Check carefully what the final price will be once you buy everything that you really need. Read the terms and conditions - you will be much happier once you accept that the airline will stick to them, and won't give you any free extras and allowances.
It's impossible to say if "it's worth taking" without knowing the price. For sure that's the only non stop flight from Venice to Barcellona.
I flew with them once last month for a domestic flight in Italy and it was a pleasant flight, no complaints at all.
Even with baggage added, we felt it was value for money. We had no problems whatsoever, flight was on time, staff were pleasant, all was good.
What I WAS impressed with was their Customer Service.
We had cause to change our flights due to an error on my part. The process was handled quickly and efficiently.....even WITH a language barrier.....and most of all, at minimal cost to us! I say go for it!
I am from Europe and have flow Vueling times some OK. Vueling ok to fly some with. No problems.
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