This work presents mass attenuation coefficients values of CuInSe2 and CuGaSe2 semiconductor thin films commonly used in photovoltaic devices. The mass attenuation coefficients were measured at different energies from 11.9 to 37.3 keV by using the secondary excitation method. Monochromatic photons were obtained using the Br, Sr, Mo, Cd, Te, Ba and Nd secondary targets. 59.5 keV gamma rays emitted from an annular Am‐241 radioactive source were used to excite secondary targets. Characteristic X‐rays emitted from secondary target were counted by a Si(Li) detector with a resolution of 0.16 keV at 5.9 keV. The measured values were compared with theoretical values calculated using WinXCOM program.