The control of the thickness and porosity of a mesoporous TiO2 layer is important to improve the photovoltaic performance of perovskite solar cells. We produced organized mesoporous TiO2 (om-TiO2) layers using a low-cost amphiphilic graft copolymer, poly(vinyl chloride)-graft-poly(oxyethylene methacrylate) (PVC-g-POEM), as a sacrificial template. This simple but effective synthetic approach generates highly mesoporous and well-organized TiO2 nanostructures with interconnected and size-Tunable features. Specifically, the average pore size increased with the amount of hydrophobic PVC main chain in the graft copolymer, which acted as the pore forming agent. Perovskite layers were prepared on top of an om-TiO2 layer according to a two-step sequential deposition: After coating the PbI2 solution in dimethylformamide (DMF) on an om-TiO2 substrate, the substrate was prewetted in isopropyl alcohol (IPA) solvent before immersing into a CH3NH3I/IPA solution. This prewetting treatment not only improves the yields of conversion from PbI2 to CH3NH3PbI3, but also increases the size of perovskite crystals with cuboid morphology. On varying the pore size and the film thickness of the om-TiO2 layer, the device performance attained 11.9% of power conversion efficiency (PCE) at pore size 70 nm and film thickness 300 nm. We measured extracted charge densities and decays of transient photovoltage to understand the kinetics of charge recombination in relation to the corresponding device performance.