I hired a couple of guys from it last year and it was a great experience.
What's the experience like as a developer? Working for Toptal is sort of my short term plan if my startup doesn't work out in fact!
So, in short Toptal seems like they do some good screening, but may be optimizing for a certain kind of developer.
I failed my initial application due to my inability to solve a couple of algorithm specific tests as other commenters have mentioned. I reappllied a couple of months later, did a couple of codility tests to ensure I'd pass this time, and flew through the rest of the process.
Yes, their signup process will potentially disquallify a couple of good devs, but it will also weed out a lot of bad devs that can't take the time to learn the solutions to common algorithm problems.
Once in, they have a variety of jobs available, some good, some bad. Overall I don't mind working for them. I've been happy with the Upwork dev's I've hired so far, so can't comment on if I'll hire through Toptal.