We determined to a degree of precision the complete set of three deformation potentials of zinc‐blende‐like (intrinsic) Inx Ga1–x P (x = 0.49) and found that their variation with chemical composition does not follow a linear rule‐of‐mixture between values of InP and GaP, as usually assumed in the published literature. Measurements were made according to a microscopic cathodoluminescence piezo‐spectroscopic (CL/ PS) procedure, previously calibrated for paradigm materials, which deformation potentials are known according to macroscopic calibration calibration procedures. The procedure followed in this study allowed us to obtain the desired deformation potential values directly on a thin film (i.e., without the need of a bulk sample), by exploiting the high spatial resolution of the electron probe. Microscopic strain fields were used, which were preliminary introduced by a pyramidal indentation print on the surface of the epitaxially grown film. The methodology enabled accurate deformation potential assessments in small material volumes for both tensile and compressive stress fields. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)