We report a novel synthesis of porous PbSe layers on Si substrates by anodic electrochemical treatment of PbSe/CaF2/Si(111) epitaxial structures in an electrolyte solution based on glacial acetic acid and nitric acid. Electron microscopy, X-ray diffractometry, and local chemical microanalysis investigation results for the porous layers are presented. Average size of the synthesized mesopores with approximately 1010 cm−2 surface density was determined to be 22 nm. The observed phenomenon of the active selenium redeposition on the mesopore walls during anodic treatment is discussed.