I actually have some experience interviewing.io. I initially starting using it as a way brush up on my technical interviewing skills (it had been years since I was last an interviewee vs. interviewer) and it ended up being through interviewing.io that I was introduced to Mattermark where I was eventually hired. It was a great tool to have in my job-hunting tool belt as I was able to 1) brush up on my tech interviewing 2) meet/network with interviewers (when an interview went well) and 3) do a few 1st round interviews with a couple of prospective companies.
I wouldn't use interviewing.io as my only means to land an interview with a company. Especially since everything is anonymous, and thus only in specific circumstances do you know the company that your interviewer is associated with. But it was a great way to do low/no risk interviews that at least had the potential to count as a first round interview.