The higher part of the park is located in the provinces of Pichincha and Imbabura and extends into Papallacta. In this area are the snow peaks Cayambe, Saraurco and Puntas with many paramo areas and rivers descending from the snow peaks. The village of Oyacachi with his thermal baths is also located in this zone. You can take walking tours from Oyacachi. The southern part of the reserve is accessible from Papallacta. You can reach the refuge on the Cayambe by jeep in good weather, but a climb to the top is dangerous and must be done with a guide.

The lower part of the park is located in the provinces of Napo and Sucumbíos along the foothills of the Eastern Andes Mountains. In this part are the very active volcano Reventador (a huge eruption in 2002 drove clouds with ash into Quito, where the airport was closed for several days), the waterfall of San Rafael and the Cofan Indian community of Sinangué.

The Reventador is accessible from El Chaco, a village on the road from Baeza to Lago Agrio.