A topological insulator (TI) is a quantum material in a new class with attractive properties for physical and technological applications. Here we derive the electronic structure of highly crystalline Sb2Te2Se single crystals studied with angle-resolved photoemission spectra. The result of band mapping reveals that the Sb2Te2Se compound behaves as a p-type semiconductor and has an isolated Dirac cone of a topological surface state, which is highly favored for spintronic and thermoelectric devices because of the dissipation-less surface state and the decreased scattering from bulk bands. More importantly, the topological surface state and doping level in Sb2Te2Se are difficult to alter for a cleaved surface exposed to air; the robustness of the topological surface state defined in our data indicates that this Sb2Te2Se compound has a great potential for future atmospheric applications.