Mid-infrared photoluminescence has been observed from interface transitions in high quality, abrupt P-Ga 0.84 In 0.16 As 0.22 Sb 0.78 /p-InAs heterojunctions grown by liquid phase epitaxy from an In-rich melt. The Ga 0.84 In 0.16 As 0.22 Sb 0.78 quaternary epitaxial layer was unintentionally doped and grown lattice matched on to a ͑100͒ oriented p-type InAs substrate, resulting in a P-p isotype heterojunction. The photoluminescence emission spectra were investigated and exhibited three pronounced emission bands in the spectral region from 0.30 to 0.68 eV; h 1 ϭ0.317 eV, h 2 ϭ0.380 eV, and h L ϭ0.622 eV. The emission band h 1 was identified with radiative transitions between electron and hole quantum well subbands in the semimetal channel at the P-GaIn 0.03 As 0.10 Sb/p-InAs interface, while the h 2 band originates from radiative transitions involving deep acceptor states in the InAs substrate. The high-energy recombination h L is characteristic of the Ga 0.84 In 0.16 As 0.22 Sb 0.78 bulk quaternary layer.