"Who's CEO" is good shorthand for "do you know who's responsible for what kind of decisions?"
IMO, it's much more efficient if each individual focuses on his domain and provides a single interface for the stakeholders for that facet of the enterprise.
The overhead of communication and context synchronization become ginormous as the organization grows and the issues affecting the enterprise grow in number if every decision is made on a flat basis. If the context synchronization is not made then the decisions made by the group will be less informed than that of an individual. For informed decisions, it would require then that each individual become an expert on the single issue discussed. This would effectively negate the main benefit of small teams - individual focus and small communications overhead.
This is not to say that flat organisations are bad. But I don't think they are a particularly good fit for the scale YC companies work at.
YC is famous for asking that question to make sure all founders wholeheartedly agree on the answer, not because they think the the other founders are any less valuable. As a founder, there are always going to be times when serious disagreements happen and at the end of the day someone has to be the overruling vote. One of the most common killers of startups is founder disputes and it's important to know who is CEO so that the company has a chance of still surviving if a founder leaves.
For example, if you have a highly technical product, the CTO might actually do way more of the talking in the interview but both sides better agree on who is CEO. It's not at all a bad sign if it's unclear based on who is the dominant speaker.