There are a lot of side discussions on the Big Bend groups about places to go when traveling to and from Big Bend National Park. Depending on the direction you are traveling, there are many places to stop, at least until you get to Marfa . Then, it gets a little light until you hit Terlingua.
I started making a map because "around Big Bend" is a relative term. There are some places here that we have already visited, and there are a number that we've been meaning to see. The main issue is that to see a lot of these places on one trip would probably require not going to the Park itself. West Texas is a big place.
We may have to visit the Big Bend area without going to Big Bend National Park. Perhaps staying in Fort Stockton as a base, rather than Terlingua.