Results of structural and electrical characteristics investigations performed for new heterostructures based on narrow-gap semiconductor ZnCdHgTe have been reported. The epilayers p-ZnxCdyHg1−x−yTe/p-Hg0.8Cd0.2Te and p-ZnxCdyHg1−x−yTe/p-Zn0.04Cd0.96Te (x = 0.10-0.13, y = 0.00-0.08) obtained by modified LPE technique of ZnCdHgTe films on substrates of (111) orientation. The detailed Hall measurements showed the formation of inverse conductivity type “channel-island” structure in subsurface region of as-grown epilayer. The study of I-V characteristics in the temperature range 177-290 K at applied voltage Va = 0-4 V shows that the carrier transport processes are caused by the recombination of majority carriers tunneling from the bulk of Hg0.8Cd0.2Te substrate material with localized states in ZnCdHgTe and by the interaction of free carriers and “potential relief” appeared as a consequence of the conductivity inversion mentioned above.