For coders - Peter Norvig's PAIP (which might be The Best Programming Book, but no room to get into that here) talks about these and leads you through building something like EMYCIN, the base of a functioning expert system without anything particularly domain-specific.
But Norvig also put them in context, and left me with the impression that Expert Systems were proven inferior to Bayesian approaches for a lot of the problems they had been developed for.
I can well imagine, though, that there are problems where expert systems are a good fit.
As an interaction model and as a way of guiding control flow, as a weird and different way of handling user interaction and building extensible applications, I think the EMYCIN example from PAIP is pretty cool. I've wondered how possible it could be to use something like EMYCIN to write webapps ...