To Darren's list and all of the other contributions I would add the following depending on how much hiking you want to do--there could indeed be an unlimited amount of opportunities at Big Bend--but there is so much that the roads may not get you to:
Slick Rock Canyon, Alto Real, Dagger Flats, Dog Canyon, The Window from below, The drive to Pine Canyon is just as good as Pine Canyon, Boquillas Canyon and the Rio Grande near it, Burro Mesa Pouroff-both from below and especially from above,--stop anywhere and you can walk around a little bit and find something (but don't for get the water and watch out for the horse crippler and the Lechuguilla and the... well, never mind!).
Frank Armstrong has a beautiful book, "Rock, River & Thorn" produced by Waterous and Co. that depicts the diversity of the area in Black and White.
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