The Sierra del Carmen dominate the views of the eastern side of Big Bend. The rugged ridge and peaks can be seen from most spots east of the Chisos and can almost always be worked into an image. There are several great locations along the Rio Grande that can be used to photograph the Carmens. My favorite might just be the small hill on the Nature Trail at Rio Grande Village. Here at the biggest campground in the park, is a small nature trail that loops out over a beaver pond and winds up up small rocky hill.
The views from the top are great both east toward the Sierra del Carmen and west toward the Chisos. This is a place that is good both at sunrise or sunset.
Or in the case of getting up there at 3am-seeing the Milky Way.
Since it was early April, I knew the Milky Way would be a band above the the peaks to the east and went with this shot in mind. A short walk from camp got me to the top of the hill and a great view of the rising Milky Way.
I set up a Canon 6D with my Bower (Samyang) 14mm f/2.8 lens. The image was ISO 12,800 for 25 seconds.
You can see this one and more in my Nightscape Galleries