Fontaine Cafe and Creperie has yummy crepes and pastries, as well as other great choices. I love this place for breakfast/brunch. Seriously.
For standard breakfast fare, and a local scene for sure, try Table Talk on Duke Street.
If you want to venture over to Del Ray, Evening Star has a great brunch.
Table Talk Restaurant
1623 Duke St, Alexandria, VA 22314
Evening Star Cafe
2000 Mt. Vernon Ave., Alexandria, VA 22301