particular polyelectrolytes due to their wettability by the perovskite precursor solution. [ 43 ] For example, Choi et al. reported a water/methanol-processed polyelectrolyte as a hole extraction material in inverted perovskite solar cells, affording a maximum PCE of 12.5%, [ 43 ] while Li et al. developed a water soluble polyelectrolyte for inverted perovskite solar cells that required thermal annealing at 140 °C for 30 min to achieve a maximum PCE of 16.6%. [ 44 ] To effi ciently extract holes from perovskite active layer and generate large built-in potential ( V bi ) across the devices, we sought a material that possesses relatively high work function ( W ) and simplifi es the preparation of high-quality perovskite layers. Recently, we found that poly(arylene-vinylene) (PAVs) with polar side chains can be synthesized by the Horner-Wadsworth-Emmons coupling/polymerization in water without using toxic reagents/catalysts. [ 45 ] This method provides an avenue to produce PAVs with a broad backbone modifi cation, especially to facilitate the introduction of electron-defi cient monomers into the polymer backbone, which lowers the highest occupied molecular orbital (HOMO) energy level of the resulting conjugated polymer and thus increases the work function of the material. [ 45 ] Also, this new method provides a route to fabricate PAVs with reasonably high molecular weight and a high degree of trans-vinylene linkages that promote planarization of the polymer backbone by removing torsional interactions between aryl-rings, thus extending conjugation. Here, we show that a PAV-based conjugated polyelectrolyte (PVBT-SO 3 ; Figure 1 a) developed through this polymerization strategy can be used as a hole extraction material for effi cient inverted perovskite solar cells that can be cast from aqueous solutions and used without thermal annealing.Fullerene/perovskite planar heterojunction solar cells, shown in Figure 1 a, were fabricated by a one-step deposition process starting from indium tin oxide (ITO) substrates (hole extracting electrode). Aqueous solutions of PEDOT:PSS or PVBT-SO 3 were spin-coated onto ITO substrates to serve as the HEL. PVBT-SO 3 formed uniform fi lms on ITO substrates, even for fi lms 5 nm in thickness, with no aggregation observable by optical microscopy ( Figure S1, Supporting Information). The perovskite precursor solution (Pb(OAc) 2 and methylammonium iodide (MAI)) was spin-coated onto an ITO/HEL substrate, followed by mild thermal annealing (at 90 °C for 5 min) to form the photoactive layer. As shown in Figure 1 b,c, uniform and continuous perovskite fi lms formed on the ITO/HEL substrates. Notably, perovskite fi lms on ITO/PVBT-SO 3 substrate had larger crystallites (crystal size տ200 nm) and were free of pinholes when compared to fi lms on ITO/PEDOT:PSS substrates. Powder X-ray diffraction ( Figure S2, Supporting Information) showed