The Fermi level position at the interface of a heterostructure is a critical factor for device functionality, strongly influenced by surface-related phenomena. In this study, contactless electroreflectance (CER) was utilized for the first time to investigate the built-in electric field in MXene/GaN structures with the goal of understanding the carrier transfer across the MXene/GaN interface. Five MXenes with high work functions were examined: Cr2C, Mo2C, V2C, V4C3, and Ti3C2. The physicochemical properties of the MXene/GaN structures were analyzed by using X-ray and UV photoelectron spectroscopies. It was shown that upon the coverage of the GaN surface by all investigated MXenes, a shift in the position of the surface Fermi level occurs, consequently raising the interface barrier. Additionally, the physicochemical stability of MXenes on the GaN surface was studied after annealing the structures at 750 °C. Our findings indicate that the annealing process increases the barrier height and the ionization energies of all studied structures. Furthermore, it has been shown that removing excess MXene material from the surface did not significantly impact the built-in electric field, emphasizing the robust physicochemical stability of the MXenes on the GaN surface. To validate the potential of engineering of MXene/GaN interface barrier, Schottky diodes with MXenes exhibiting the highest barrier height (Mo2C and V2C) were demonstrated.