This study investigated the relationship between the superconducting properties, electrical properties, sputtering process parameters, and post-growth annealing of NbN films. Four series of NbN films were deposited by DC magnetron sputtering using different process parameters. With the assistance of a four-probe method, the superconducting performance presented first an increase and then a decreasing trend as the resistance of the prepared films increased, which could be attributed to the variation of the N/Nb ratio in the films. This correlation implied that it is very challenging to fabricate films with both high Tc and high resistance or high Tc and low resistance by adjusting the sputtering process parameters. In order to overcome these bottlenecks, a series of films were deposited on Si, GaN/Si, SiN/Si, AlN/Si, and AlN/sapphire substrates, and the film deposited on Si was annealed at 900 °C. Annealing reduced the stress of the films on the buffer layer and increased the grain size and crystallinity of the films, except for the films on the GaN/Si substrates. This resulted in a significant decrease in the resistivity of the film and a significant increase in the superconducting transition temperature.