Semiconductor heterostructures based on layered two-dimensional transition metal dichalcogenides (TMDs) interfaced to gallium nitride (GaN) are excellent material systems to realize broadband light absorbers and emitters due to their close proximity in the lattice constants. The surface properties of a polar semiconductor such as GaN are dominated by interface phonons, and thus the optical properties of the vertical heterostructure are influenced by the coupling of these carriers with phonons. The activation of different Raman modes in the heterostructure caused by the coupling between interfacial phonons and optically generated carriers in a monolayer MoS2–GaN (0001) heterostructure is observed. Different excitonic states in MoS2 are close to the interband energy state of intraband defect state of GaN. Density functional theory (DFT) calculations are performed to determine the band alignment of the interface and revealed a type-I heterostructure. The close proximity of the energy levels and the excitonic states in the semiconductors and the coupling of the electronic states with phonons result in the modification of carrier relaxation rates. Modulation of the excitonic absorption states in MoS2 is measured by transient optical pump-probe spectroscopy and the change in emission properties of both semiconductors is measured by steady-state photoluminescence (PL) emission spectroscopy. There is significant red-shift of the C excitonic band and faster dephasing of carriers in MoS2. However, optical excitation at energy higher than the bandgap of both semiconductors slows down the dephasing of carriers and energy exchange at the interface. Enhanced and blue-shifted PL emission is observed in MoS2. GaN band-edge emission is reduced in intensity at room temperature due to increased phonon-induced scattering of carriers in the GaN layer. Our results demonstrate the relevance of interface coupling between the semiconductors for the development of optical and electronic applications.