(Note: I realize this is close to http://stackoverflow.com/questions/186392/how-do-you-document-your-database-structure , but I don't think it's identical.)
I've started work at a place with a database with literally hundreds of tables and views, all with cryptic names with very few vowels, and no documentation. They also don't allow gratuitous changes to the database schema, nor can I touch any database except the test one on my own machine (which gets blown away and recreated regularly), so I can't add comments that would help anybody.
I tried using "Toad" to create an ER diagram, but after leaving it running for 48 hours straight it still hadn't produced anything visible and I needed my computer back. I was talking to some other recent hires and we all suggested that whenever we've puzzled out what a particular table or what some of its columns means, we should update it in the developers wiki.
So what's a good way to do this? Just list tables/views and their columns and fill them in as we go? The basic tools I've got to hand are Toad, Oracle's "SQL Developer", MS Office, and Visio.