Optical refrigeration, or laser cooling of solids1, offers a cryogen-free route to temperature control for quantum and electronic systems. Existing progress2,3,4,5,6,7,8 relies on a phonon-assisted up-conversion photoluminescence approach, which remains constrained by stringent material and excitation requirements. Here we demonstrate a distinct route, interfacial-charge-transfer-driven optical cooling, in two-dimensional semiconductor heterostructures. Photo-excited carriers in WSe2 cross a type-II junction into MoSe2 or WS2, extracting lattice energy nonradiatively—through a phonon-assisted interfacial charge transfer process. Raman and photoluminescence measurements show prominent low-temperature signatures in the WSe2 layer, with transient absorption spectroscopy identifying a phonon-assisted, barrier-activated interlayer charge transfer. Molecular dynamics simulations show a prominent interfacial thermal resistance sustaining the temperature gradient. This barrier-mediated phonon extraction bypasses the need for near-unity quantum efficiency or resonant excitation, offering a promising strategy for cryogen-free refrigeration and thermal management in quantum, optoelectronic and nanoscale systems.