I was resistant at first also. When I first picked up Zope in 1998, the first thing I asked was if I could store all of my data in MySQL. I didn't know what I was missing yet, but I'm glad it only took me one project to realize the true strength of using a Object Oriented Database with an Object Oriented application server.
Things have come a long way since then, and now it could even be considered trendy to be using an Object Oriented Database. Is the Relational Database Doomed? is a decent article that outlines some of the big benefits people are seeing today using OODBs.
Zope was just way ahead of their time, but now they have the benefit of experience behind them as they continue to develop on the ZODB. Out of the box the ZODB comes packed with features and tools to help manage itself such as hot incremental backup tools and full blob support now as of ZODB 3.8.
Another big benefit for me is not dealing with the database much at all. As a Zope developer, most of the time I don't even notice it is there since it handles things like transactions fairly transparently. I don't have to deal with the extra layer of an ORM or manually do SQL joins to gather my objects up. I can also establish relationships between objects purely based on their proximity to other objects in the database.
So I think that Zope made the right choice long, long ago. We still use RDBMSes when it makes sense, but the ZODB and OODBs in general are a great choice for content driven applications.