It's easy for candidates to exaggerate or misrepresent their accomplishments. This is especially true when they worked on large team projects. For example, if they say "I was part of the team that built Google Search", that could be a really impressive thing if they played a key leadership or technical role, or it could be a really unimpressive thing if they hung out while others did the heavy lifting, and it's very hard to tell the difference.
In addition, there are levels of technical chats that become very difficult to fake, further reducing the pool of lying interviewees people claim to be defending against.
There are tradeoffs, but I found it to be an overall net positive in addition to the technical assessment. Doing this effectively requires that the interviewer have a pretty broad exposure to lots of different technology, otherwise you can't distinguish between someone BSing their role vs something you just don't know a lot about / can't ask intelligent questions about. It's also incredibly subjective, which would make me hesitant to rely on it without more objective criteria.
That's a pretty idealistic view of people. Most people exaggerate on their resume. The most reliable tool (at the moment) to cut through and establish some common metrics is the technical test. How do you compare technical "chats" between individuals? Duration of call? Gut feel? How do you ensure that the person on the phone has the breadth and depth of experience to thoroughly discuss any and all projects on the phone with the interviewee? Is it the same person on all of these calls? It can't be, so how would you compare between two interviewers' subjective feedback?
> This is not without cost to the employer...
This is a HUGE cost, especially at a startup. A mis-hire at a startup can sink the entire ship.
I do think that your approach has merit, and I personally dislike technical interviewing, but for a startup the OP's approach is, IMO, the best tradeoff.
It's the "eventually" part that's problematic, since it can be long, uncomfortable, and expensive to the company.