Most key-value databases didn't prove (as in: show me actual resistance tests, not supercompany123 uses it) that they are reliable. The day they do, I'll be the first one to use them. Until then, it's just a toy for devs who don't want to deal with ER models.
Then again, Postgres -- the project -- did not try to position itself (was there even such a thing as "positioning" for Postgres 16 years ago?) as a mature, stable project that one would credibly bet one's business on.
Lots of early database releases are going to be like Mongo, the question is how much the parties at play own up to the fact that their implementation is still immature and present that starkly real truth to their customers. So far, it seems commercial vendors are less likely to do that.
However, actually-not-a-terrible-idea is pretty relative, when you look at how the industry has evolved in the mean time. I mean, compared to MySQL at the time, PostgreSQL 6.5 was really not a terrible idea. 7.3 was the first release I didn't have to use MySQL as a prototyping system though.
And with 9.x things are getting even better.