While perovskite solar cells (PSCs) have been developed with different device architectures, mesoporous devices have provided the highest power conversion efficiencies. In this work, the working mechanism of both positive-intrinsic-negative (p-i-n) and negative-intrinsic-positive (n-i-p) meso-superstructured (MSSC) PSCs, which include a thin interlayer of porous alumina at the bottom electrode, is explored. Interestingly, for both p-i-n and n-i-p architecture, the mesoporous configuration was more efficient than its planar counterpart. For MSSC SnO2-based n-i-p devices, that result was primarily due to an increase in Voc and Jsc, resulting from improved band alignment and filling of the electron trap states (n-doping at the SnO2/perovskite interface), which led to devices with 21.0% efficiency and 20.3% stabilized power output (SPO). Although MSSC NiOx-based p-i-n meso-superstructured devices were less efficient due to lower Voc, a slightly higher Jsc and fill factor improvement was achieved by the Al2O3 mesoporous layer, resulting in devices with 16.9% efficiency. Importantly, the electronic nature of the perovskite is dependent upon its physical confinement within a mesoporous scaffold. Therefore, either p- or n-type semiconductor/perovskite interfaces can be engineered by selectively modifying the semiconductor behavior with the introduction of an insulating mesoporous scaffold interlayer.