The Zoe is a 33 000 € car brand new. Cars must start somewhere before a used market show up to cheapen them further. This one will be even cheaper down the road once it appears in the used market.
As for who uses it, I know plenty of people who own one to do things like small size deliveries, citroen sells a version of this car that doesn't have a passenger seat for the sake of more cargo capacity. It's a pretty nifty car to have as long as you mostly drive it within the city, where most streets don't allow you to go past 30 kilometer per hour. For city dwellers in Europe, it works plenty fine and better than cars that are too big for some of the parking spots you might have taken with a small one like the ami.