Solid-state perovskite solar cells have been expeditiously developed since the past few years. However, there are a number of open questions and issues related to the perovskite devices, such as their long-term ambient stability and hysteresis in current density-voltage curves. We developed highly efficient and hysteresis-less perovskite devices by changing the frequently used TiO mesoscopic layer with polymer-hybridized multidoped ZnO nanocrystals in a common n-i-p structure for the first time. The gradual adjustment of ZnO conduction band position using single- and multidopant atoms will likely enhance the power conversion efficiency (PCE) from 8.26 to 13.54%, with PCE = 15.09%. The highest PCE of 13.54% was demonstrated by 2 atom % boron and 6 atom % fluorine co-doped (B, F:ZnO) nanolayers (using optimized film thickness of 160 nm) owing to their highest conductivity, carrier concentration, optical transmittance, and band-gap energy compared to other doped films. We also successfully apply a fine polyethylenimine thin layer on the doped ZnO nanolayers, causing the reduction in work function and overall demonstrating the enhancement in PCE from ∼10.86% up to 16.20%. A polymer-mixed electron-transporting layer demonstrates the remarkable PCE of 20.74% by decreasing the trap sites in the oxide layer that probably reduces the chances of carrier interfacial recombination originated from traps and thus improves the device performance. Particularly, we produce these electron-rich multidoped ZnO nanolayers via electrospray technique, which is highly suitable for the future development of perovskite solar cells.