The Volt makes no sense to me. If I could afford the Volt price tag then I honestly wouldn't give 2 craps about gas mileage (I hardly do right now). In that price bracket I would be looking at premium mid-sized or full sized cars. Maybe a used M3 or S4. I dunno. I do know that MPG would not be an issue for me on a newer vehicle.
Heh, well, the Volt's charge sustain mileage isn't very good at an EPA rated 37 mpg combined.

And, the 4 seater compact Volt requires premium vs. the 50 mpg combined 5 seater (not comfortably) midsized Prius...
It is goofy that yes, the Volt's price tag is fairly high. One's getting up into low end luxury car pricing territory and Chevy doesn't have the brand cachet of Lexus, BMW, Audi, Mercedes, etc.
Many buyers of the Volt and Leaf are early adopters and simply want to reduce their dependence on oil, esp. foreign oil and reduce their GHG emissions. Some have PV (photovoltaic) panels on their roof and some live in areas where lots of electricity comes from renewable sources like hydro.
Perhaps another way of looking at it is that some people are willing to pay for a luxury brand, higher end car or certain features (e.g. sunroof, bigger engine, gadgets like heated/cooled seats, massage seats, rear footrests, DRCC, LKA, LKW, etc.) Those things don't save you any money. There's no "payback" period. This is just a feature that lets you use less oil and potentially emit fewer greenhouse gases.
I also do suspect that Volt demand will pickup or at least stay level (instead of falling) in CA because of
http://www.autoblog.com/2011/11/16/chevy-volt-ready-for-california-hov-access-extra-1-500-in-reba/. Unlike the Leaf, the '11 Volt didn't meet emissions standards and warranty requirements to qualify for the white HOV stickers nor CVRP (rebate).
I do see a case for the Volt vs. say the Leaf in that if you buy a pure EV, you will need a 2nd car (gas or diesel). For the 2nd car, you'll need to pay for fuel, maintenance, insurance and have it depreciate. At least w/the Volt, you won't need the 2nd car due to range limitations but unfortunately, it means some compromises (interior capacity, price, premium fuel and not so good mileage).