Hole‐transporting layer‐free mesoporous carbon (mC) architectures represent a printable, low‐cost and stable solution for the future commercialization of perovskite solar cells (PSCs). CsPbI3 perovskite is attracting attention for its inorganic structure, which yields higher structural stability compared to hybrid counterparts and allows reversibility of its photoactive phase. Here the photovoltaic performance of large‐area (144 mm2) mC devices infiltrated with CsPbI3:EuCl3 is systematically evaluated, using AVA‐MAPbI3 mC‐PSCs as a reference. Measured and simulated J‐V curves acquired at various scan rates show a significantly reduced hysteresis for Eu‐doped CsPbI3 with respect to AVA‐MAPbI3 mC‐PSCs. The synergic comparison between experiments and simulations reveals the complex interplay between ionic and electronic charges in the two mC‐PSCs, supporting the argument that cation migration is suppressed in the CsPbI3:EuCl3 mC‐PSCs. This also agrees with steady‐state photoconversion efficiency measured and simulated at fixed bias, characterized by a constant value over time in CsPbI3:EuCl3, contrary to what occurs in AVA‐MAPbI3 where a decay arises from enhanced ionic migration. In addition, CsPbI3:EuCl3 mC‐PSCs maintain their initial efficiency up to 250 hours at 55°C under continuous illumination during maximum power point tracking measurements. The possibility of reusing the CsPbI3:EuCl3 mC‐PSCs multiple times is demonstrated, pointing out the superiority of this inorganic perovskite in terms of sustainability.This article is protected by copyright. All rights reserved.