I've discussed this extensively with some sysops from Facebook in the past.
Facebook primarily uses MySQL for structured data storage. For instance, wall posts, user information, etc. are all stored in MySQL. They replicate this between their various data centers.
For blob storage (photos, video, etc.), Facebook makes use of a custom solution that involves a CDN (fbcdn) externally and NFS internally.
For a few means of document storage and write-heavy applications (such as inbox search), Cassandra is used. Contrary to popular belief, Cassandra is NOT the primary database at Facebook. In fact, it isn't anywhere close to being the primary database platform; it used for very specific scenarios where the NoSQL paradigm fits best.
Hope this helps
EDIT:
I should also note that this is by no means the full extent of technologies that FB uses, but it does represent the vast majority of storage that they take advantage of.