Record power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) have been obtained with the organic hole transporter 2,2′,7,7′-tetrakis( N , N -di- p -methoxyphenyl-amine)9,9′-spirobifluorene (spiro-OMeTAD). Conventional doping of spiro-OMeTAD with hygroscopic lithium salts and volatile 4- tert -butylpyridine is a time-consuming process and also leads to poor device stability. We developed a new doping strategy for spiro-OMeTAD that avoids post-oxidation by using stable organic radicals as the dopant and ionic salts as the doping modulator (referred to as ion-modulated radical doping). We achieved PCEs of >25% and much-improved device stability under harsh conditions. The radicals provide hole polarons that instantly increase the conductivity and work function (WF), and ionic salts further modulate the WF by affecting the energetics of the hole polarons. This organic semiconductor doping strategy, which decouples conductivity and WF tunability, could inspire further optimization in other optoelectronic devices. A radical doping approach In perovskite solar cells, high power conversion efficiencies (PCEs) are usually obtained with an organic hole transporter called spiro-OMeTAD. This material must be doped to have sufficient conductivity and optimal work function, but the conventional process with lithium organic salts requires a long oxidation step that also affects device stability. Zhang et al . added spiro-OMeTAD biradical precursors that convert into stable organic monoradicals. Combined with ionic salts, this doping strategy formed solar cells with high PCEs (>25%) and improved stability. This approach also allows conductivity and work function to be tuned separately and could be applied in other optoelectronic devices. —PDS Organic radicals and ionic salts enable doping of an organic hole transporter without post-oxidation treatments.