A molecular level approach is presented for low-temperature electrosynthesis of compound semiconductor films from a single electrolyte. This paper outlines the concepts underlying molecular layer electrodeposition and underscores its unique features. It presents the results of initial investigations for the synthesis of Cu-In-Se based films, revealing new process parameters to manipulate the film stoichiometry and microstructure. The approach combines the advantages of electrodeposition with the atomic level control of epitaxial deposition, extending their utility to device fabrication with simpler apparatus and practical deposition rates. (C) 2002 The Electrochemical Society.