Hole conductor-free printable mesoscopic perovskite solar cells (p-MPSCs), comprising m-TiO₂/m-ZrO₂/C triple mesoscopic layers, have emerged as a promising photovoltaic technology for commercial applications because of their low cost, easy operation, and outstanding stability. However, p-MPSCs suffer from a considerable open-circuit voltage (V_OC) loss compared with traditional PSCs, resulting in a discernible disparity in power conversion efficiency (PCE) between p-MPSCs and traditional PSCs. In this article, we present a novel approach employing 5-amino-4-carboxamide imidazole hydrochloride (AICA) to enhance V_OC of p-MPSCs. AICA demonstrates a dual function, encompassing the regulation of the work function of the perovskite film and effective passivation of the uncoordinated Pb²⁺ and I⁻ defects within the perovskites. Consequently, the introduction of AICA stabilizes the structure of the perovskites, leading to the formation of high-quality perovskite films and effectively inhibiting defect-induced nonradiative recombination. Owing to the incorporation of AICA, notable improvements in the photovoltaic performance of p-MPSCs are observed, with a considerable increase in PCE from 14.21% to 16.68% and a corresponding rise in V_OC from 0.88 to 0.98 V.