The formation chemistry and growth dynamics of thin‐film CuInSe2grown by physical vapor deposition have been considered along the reaction path leading from the CuxSe:CuInSe2two‐phase region to single‐phase CuInSe2. The (Cu2Se)&bgr;(CuInSe2)1−&bgr;(0<&bgr;≤1) mixed‐phase precursor is created in a manner consistent with a liquid‐phase assisted growth process. At substrate temperatures above 500 °C and in the presence of excess Se, the film structure is columnar through the film thickness with column diameters in the range of 2.0–5.0 &mgr;m. Films deposited on glass are described as highly oriented with nearly exclusive (112) crystalline orientation. CuInSe2:CuxSe phase separation is identified and occurs primarily normal to the substrate plane at free surfaces. Single‐phase CuInSe2is created by the conversion of the CuxSe into CuInSe2upon exposure to In and Se activity. Noninterrupted columnar growth continues at substrate temperatures above 500 °C. The addition of In in excess of that required for conversion produces an In‐rich near‐surface region with a CuIn3Se5surface chemistry. A model is developed that describes the growth process. The model provides a vision for the production of thin‐film CuInSe2in industrial scale systems. Photovoltaic devices incorporating Ga with total‐area efficiencies of 14.4%–16.4% have been produced by this process and variations on this process. ©1995 American Institute of Physics.