There is a bit of open-source software out there but Visio Professional's tool for reverse-engineering database schemas is quite good because it de-couples the process of reverse-engineering and diagramming. I use this a lot because it tends to be readily available at most sites.
One nice feature of visio is that you can reverse engineer and then construct your own diagrams from the reverse-engineered schema. Doing this is a very good way to explore the schema and understand it as you are doing this work as a part of interactively building a reference document for the schema. I've used this technique to reverse engineer everything from Activity Based Costing Systems to Insurance Underwriting Systems, typically without much help from the vendor. Tinkering about with Visio diagrams is quite relaxing.
Between this and a little hypothesis testing about FK relationships (If the FK is not physically present on the table) you can make sense of quite complex schemas. I've found this diagramming approach makes Visio a head-and-shoulders leader because you can easily interact with the reverse-engineered model in a fairly convenient way. You can fill in missing foreign keys, build subject area diagrams and add annotations on the diagrams. The interactivity of this process makes it a good learning tool.
This is a somewhat subjective view but the interactivity works very well as a learning proces for me and it's by far my preferred approach. Most sites won't begrudge you the £300 or so for a license - if they don't already have it available. The only site I ever worked where they had to get it in was because they had Visio Standard instead of Pro. I asked nicely and the PHB signed it off.
