The valence and conduction band offsets (VBO and CBO) at the semiconductor heterojunction are crucial parameters to design the active region of contemporary electronic and optoelectronic devices. In this report, to study the band alignment parameters at the In0.15Al0.85N/MoS2 lattice matched heterointerface, large area MoS2 single layers are chemical vapor deposited on molecular beam epitaxial grown In0.15Al0.85N films and vice versa. We grew InAlN having an in-plane lattice parameter closely matching with that of MoS2. We confirm that the grown MoS2 is a single layer from optical and structural analyses using micro-Raman spectroscopy and scanning transmission electron microscopy. The band offset parameters VBO and CBO at the In0.15Al0.85N/MoS2 heterojunction are determined to be 2.08 ± 0.15 and 0.60 ± 0.15 eV, respectively, with type-I band alignment using high-resolution x-ray photoelectron spectroscopy in conjunction with ultraviolet photoelectron spectroscopy. Furthermore, we design a MoS2 quantum wel...