The surface defects and grain boundary defects of organometallic halide perovskite films are detrimental to both the efficiency and stability of perovskite solar cells (PSCs). Furthermore, the electrical conductivity, work function and surface morphology of the hole transport layer (HTL) can also affect the performance of PSCs significantly. Here, we first have developed a novel synergistic strategy that uses multiple functional EMIC (1-Ethyl-3-methylimidazolium chloride) ionic liquid to modify PEDOT:PSS (poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate) HTL, thereby obtaining the HTL with high electrical conductivity, low work function and smooth surface. Moreover, a novel S-acetylthiocholine chloride molecule which replaces expensive PCBM (phenyl-C61-butyric acid methyl ester) is developed to effectively passivate the negative- and positive-charged ionic defects in hybrid perovskite. The synergistic strategy extends the carrier recombination lifetime and reduces the charge trap density. In addition, the current hysteresis of the inverted device was also effectively eliminated. As a result, the champion cell in small area shows 20.06% efficiency with no hysteresis, along with an efficiency 18.77% for inverted PSCs in an active area of 1 cm2, both of which are the highest efficiency in the one-step PEDOT:PSS-based inverted PSCs so far. Compared to PCBM, the device passivated by S-acetylthiocholine chloride also has improved environmental stability (retaining 85% of initial PCE after 35 days storage without encapsulation in air with 60% humidity) and thermal stability (retaining 87% of initial PCE after 80 °C for 24 h storage without encapsulation under inert atmosphere).