The chemical compounds present on the surface of CdTe have been investigated after different surface preparations and correlated with the properties of junctions formed by Cr on the CdTe. X‐ray photoelectron spectroscopy (XPS) analysis indicates that four different surface compositions result from five different treatments. Cleaving leaves a stoichiometric surface whereas oxidation in air leads to the formation of TeO2. Bromine‐in‐methanol etch leaves a Te‐enriched surface and chromate etch leaves a surface containing both TeO2and excess Te. Hydrogen heat treatment of an etched CdTe surface restores a stoichiometric cleavedlike surface from that disrupted by the etching process. Effects on the properties of subsequently formed junctions are evidenced by a decrease in the diode saturation current from 2×10−5for a bromine‐etched surface to 2×10−8A/cm2for a cleaved surface.