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[–] Amadameus ago 

The short answer is that yes, all compounds give off some kind of vapor. You just need extremely sensitive methods at extremely low vacuums to find it.

The long answer is that in extreme cases like this, our definition of 'gas' and even 'matter' starts to get difficult.

What is a gas? Just atoms flying around unbound to each other, right? Well once you get down to a very deep vacuum this starts to become individual atoms, like a countable number, in the space.

What about some pieces of a larger molecule that broke off spontaneously and will re-attach to the surface of our sample as soon as it touches it again? Was that a gas, or some kind of unstable breakdown compound?

It gets weird.