Hmmm so are you saying that you intend to drive 200 miles to buy the Volt and you'd like to drive back with at least 50% EV miles?
I mean, if you want to you really could.

Personally, I wouldn't bother. The electric motor is for every day driving, the ICE is for long distance driving.
If the Volt had a quicker L2 charging rate then I'd say go for it... take a long lunch break on your way back! But it only charges at 3.3 kW. If you've been driving highway speeds the whole way, the Volt will only charge about 10 miles / hour. Waiting 4+ hours to eek out 45 electric miles to save 1 gallon of gas isn't worth it.