inkscape
+1 for inkscape
It comes in handy for all kinds of block diagrams and illustrations. I use it often, for example for drawing UML diagrams instead of learning a dedicated tool. Gives output in nice vector formats, and allows you to create re-usable groups and use a snapping grid, which makes it really easy to draw schematics.
For more "blocky" block diagrams, I may just use MS Power-Point.