AlGaN/4H–SiC heterojunction diodes with varying composition of Al have been fabricated. Five different compositions were investigated, GaN, Al0.1Ga0.9N, Al0.15Ga0.85N, Al0.3Ga0.7N, and Al0.5Ga0.5N, along with a 4H–SiC homojunction diode for comparison. The turn on voltage was around 1 V, and the ideality factor between 1 and 2 for all heterojunction diodes except for the Al0.3Ga0.7N diode. This diode had an ideality factor between 2 and 3, and also showed a much lower series resistance, indicating a change in transport mechanism across the junction. A tunnel assisted recombination model was analyzed and compared to the extracted values of the GaN diode. The model agreed well with both current–voltage and capacitance–voltage measurements for this diode. This model was not applied to the other samples, since their characteristics could not be explained by a simple mechanism.