In this study, we introduce a new concept for the highly efficient tandem p-n photoelectrochemical cell consisting of coumarin6 organic dye-anchored p-type CuCrO2 delafossite semiconductor as photocathodes coupling with traditional n-type TiO2 based photoanodes. Also, we have systematically studied the photovoltaic performance of tandem cells as a function of post-annealing of CuCrO2 films before sensitization. Hydrothermally synthesized CuCrO2 nanocrystals exhibited a high surface area with small crystallite size of 12 nm, phase-pure and well-crystalline after the optimized post-annealing conditions. The experimental results indicated that the optimal post-annealing temperature was 450 degrees C for 1 h due to the larger active surface area, lower R-th and higher J(sc) and V-oc, values. This tandem cell, fabricated by employing the CuCrO2 photocathodes, iodide-based redox mediator and a coumarin6 organic dye, afforded an impressive efficiency of 2.33% with V-oc of 813 mV, J(sc) of 4.83 mA cm(-2), and fill factor of 0.59. The obtained parameters are acceptably high in comparison to NiO photocathode-based tandem cells previously reported in literature under similar experimental conditions. Therefore, this work opened the way for developing highly-efficient tandem photoelectrochemical solar cells.