Direct stacking of n‐type and p‐type metal oxide (MOx) semiconductors is one of the appealing directions toward low cost and environmentally friendly photovoltaics (PVs). However, the main shortcoming, hindering the PV performance of MOx heterojunction devices is attributed to the tradeoff between light absorption and maximized carrier extraction in p‐type MOx. In this work, we demonstrate that the nanorod (NR) geometry of Co3O4 light absorber with a nearly ideal bandgap of ∼1.48 eV, can remove this hurdle through strong internal light trapping of adjacent one‐dimensional (1D) structure and enhanced carrier mobility. The inverted n‐on‐p configuration of the core‐shell 1D heterojunction, obtained by depositing a thin TiO2 n‐type layer, resulted in enlarged charge generation compared to the typical p‐on‐n counterpart device. Fine‐tuning of Co3O4 NRs length, permits PV investigation of the heterojunctions with respect to absorber layers thickness. The optimized Co3O4 NRs/TiO2 heterojunction (30 nm Co3O4NR length) presented a record high open circuit photovoltage (Voc) of (0.52 ± 0.03) V under 1 sun irradiation. Impedance analysis of the heterojunctions, indicates formation of the p+‐p depletion. The presented work can highlight some vital venues to enhance photoconversion efficiency of the all‐oxide heterojunctions while introducing a pioneer contender as inverted (n‐on‐p) MOx heterojunction.