NbTiN thin films are promising candidates for superconducting multilayer structures aimed at surpassing the intrinsic field limits of bulk Nb in superconducting radio-frequency (SRF) cavities. In this work, films grown by plasma-enhanced atomic layer deposition were systematically investigated with respect to their crystalline structure, surface morphology, and field emission behavior in their as-deposited state, as well as after annealing in vacuum at and , respectively. X-ray diffraction reveals that annealing induces significant grain growth, a pronounced (111)-texture, and a strong reduction of residual stress, with the samples exhibiting the most uniform and relaxed microstructure. Optical profilometry shows a clear decrease in macroscopic roughness by approximately 20%–25% after annealing, while atomic force microscopy measurements confirm that the nanoscale roughness remains low and largely unaffected by the heat treatments. Field emission scanning microscopy demonstrates that annealing substantially increases the onset field for electron field emission from values below in the as-deposited state to for annealed films, correlating with improved crystallinity, reduced stress, and enhanced film-substrate adhesion. Complementary ultraviolet photoelectronspectroscopy measurements yield a work function of , supporting the interpretation of the field emission scanning microscope data. The combined results show that high-temperature annealing, particularly at , significantly enhances the structural and functional performance of NbTiN films, underscoring their potential for application in superconducting multilayer coatings for next-generation SRF cavities.