Blockchains are an immutable ledger, meaning any data initially entered onto them can’t be altered. Yen realized that putting users’ public keys on a blockchain would create a record ensuring those keys actually belonged to them – and would be cross-referenced whenever other users send emails. “In order for the verification to be trusted, it needs to be public, and it needs to be unchanging,” Yen said.
The benefit of doing this with a blockchain instead of a privately held and maintained database is that the latter can be compromised, and you just have to trust "whoever" is maintaining that private database. Blockchain means that the ledger is distributed to many nodes, and any post-entry modification to that chain would be instantly recognized, and marked invalid by the other nodes operating the chain. Besides that, when you're looking up a public key for a recipient on such a blockchain, you would be looking it up at a number of nodes large enough that in order for a malicious entry to come through, they would all have to be modified in the same way, at the same time, and you would have to be asking before the change got flagged. Poisoning blockchain data like this is simply not possible; that's what makes this an especially secure option.