The structural and photoelectrical properties of Al-doped ZnO (AZO)/SiC/p-Si and AZO/SiC/n-Si heterojunctions, fabricated at low temperature by pulsed laser deposition, were investigated by means of a number of techniques. Raman analysis indicates that SiC layers have the cubic 3C-SiC phase, whilst X-ray diffraction measurements show that AZO films exhibit a hexagonal wurtzite structure, highly textured along the c-axis, with average crystallites size of 35.1 nm and lattice parameter c of 0.518 nm. The homogeneous and dense surface morphology observed by scanning electron microscopy was confirmed by atomic force microscopy images. Moreover, UV–Vis-NIR spectra indicated a high transmittance of SiC films in the region 550–2500 nm, about 80% transmittance of AZO films in the 450–1000 nm region, and optical band gaps in good agreement with literature. These results prove that pulsed laser deposition is a low-cost technique suitable to grow SiC and AZO films with excellent material properties. The effect of the Si doping on the current transport mechanisms in the heterojunctions was investigated by current-voltage measurements under dark and white light illumination. Both heterojunctions exhibit a diode behaviour and relatively low leakage current, with a noticeable superiority for the AZO/SiC/n-Si device also under illumination, with an illumination/dark ratio of about 400. Our results indicate that the AZO/SiC/p-Si heterojunctions, with higher values of ideality factor, series resistance and lower rectifying ratio, have a complex current transport compared to the diodes grown on n-type Si. Additionally, capacitance-voltage measurements and Mott-Schottky plot allowed to determine a built-in potential of 0.51 V for the Al/AZO/SiC/p-Si/Al device.