The effect of post-growth annealing treatment of zinc oxide (ZnO) nanorods on the electrical properties of their heterojunction diodes (HJDs) is investigated. ZnO nanorods are synthesized by the low-temperature aqueous solution growth technique and annealed at temperatures of 400 and 600°C. The as-grown and annealed nanorods are studied by scanning electron microscopy (SEM) and photoluminescence (PL) spectroscopy. Electrical characterization of the ZnO/Si heterojunction diode is done by current–voltage (I–V) and capacitance–voltage (C–V) measurements at room temperature. The barrier height (ϕB), ideality factor (n), doping concentration and density of interface states (NSS) are extracted. All HJDs exhibited a nonlinear behavior with rectification factors of 23, 1,596 and 309 at ±5 V for the as-grown, 400 and 600°C-annealed nanorod HJDs, respectively. Barrier heights of 0.81 and 0.63 V are obtained for HJDs of 400 and 600°C-annealed nanorods, respectively. The energy distribution of the interface state density has been investigated and found to be in the range 0.70 × 1010 to 1.05 × 1012 eV/cm2 below the conduction band from EC = 0.03 to EC = 0.58 eV. The highest density of interface states is observed in HJDs of 600°C-annealed nanorods. Overall improved behavior is observed for the heterojunctions diodes of 400°C-annealed ZnO nanorods. © 2021 Sadia Muniza Faraz et al.