| Summary: | Fully printable carbon-based multiporous-layered-electrode perovskite solar cells (MPLE-PSCs) are easy to fabricate and have excellent durability. In this study, the porosity of the mesoporous TiO<sub>2</sub> layer as the electron transport layer in MPLE-PSCs was controlled by varying the particle diameter of TiO<sub>2</sub> nanoparticles from 14 nm to 98 nm. Furthermore, the results of absorbed photon-to-current conversion efficiency, visible light reflectance spectroscopy, pore-size distribution, X-ray diffraction, field emission scanning electron microscopy, and photovoltaic parameters of MPLE-PSCs are discussed. Although the porous TiO<sub>2</sub> layer with smaller nanoparticles showed higher photoabsorption, it was found that the more voids of perovskite crystals created in the TiO<sub>2</sub> porous layer, the smaller the particle size (<18 nm). The porous TiO<sub>2</sub> layers with particles over 26 nm are well filled with perovskite crystals, resulting in a higher photovoltaic capacity with TiO<sub>2</sub> particles over 26 nm. As a result, the short-circuit current density (<i>J</i><sub>SC</sub>) showed a maximum value using 43 nm TiO<sub>2</sub> particles, with an average power conversion efficiency (PCE) of 10.56 ± 1.42%. Moreover, the PCE showed a maximum value of 12.20% by using 26 nm TiO<sub>2</sub> nanoparticles.
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