Hybrid perovskite solar cells have attracted tremendous interest in the photovoltaic community. Despite their high defect tolerance, reducing the trap density by material engineering and surface modification is still critical to further boost performance. Here, methylammonium lead(II) iodide perovskite has been doped with imidazolium iodide in high concentrations (10-30 mol%) to boost solar cell performance, by passivating defects. Fumigation with methylamine results in the deprotonation of the embedded imidazolium cations, generating imidazole and methylammonium cations. The resulting (neutral) imidazole is extruded from the 3-D perovskite crystal and distributes around the crystal leading to auto-passivation of crystal defects. The structure of the imidazolium-PbI3 salt intermediate (i.e. formed in the absence of the methylammonium cation) has been determined and the resulting perovskite film characterized. Employed in solar cells, a power conversion efficiency (PCE) up to 20.14% is demonstrated.