Infrared cooled photodetectors must operate at higher temperatures to reduce their size, weight and power consumption (SWaP context). Their stability and image quality are then challenged by extra electrical activity of crystal defects. Knowledge of defect populations is mandatory to improve the material quality of the epitaxial Hg1−xCdxTe (MCT) active layer and the Cd1−xZnxTe (CZT) substrate. Positron annihilation spectroscopy with a slow positron beam was used to study near-surface open-volume defects profiles. Low- and high-momentum fractions (S,W) were used to characterize the Doppler broadening of the 511 keV electron-positron pair annihilation-line as a function of the positron implantation energy E. The results show that three regions can be identified beneath the surface of the as-grown non-optimized MCT layer. The quasi-linear relationship between the annihilation characteristics in the regions suggests that the defect populations mainly correspond to the same open-volume defect in different concentrations. The probed defect is thought to be related to the mercury vacancy. This hypothesis is discussed in an original way with near-surface elemental profiles using scanning transmission electron spectroscopy combined to energy dispersive x-ray spectroscopy (STEM-EDX). Afterwards, this approach is extended to CZT substrates showing that surface and bulk properties of those fabricated by LYNRED tend to match those that are state-of-the-art. A common open-volume defect is probed, in concentration estimated by Hall effect around 1015 cm−3 and thought to be related to the cadmium vacancy.