A new non-conjugated polymer (PVCz-OMeDAD) with good solution processability was developed to serve as an efficient dopant-free hole-transporting material (HTM) for perovskite solar cells (PSCs). PVCz-OMeDAD was simply prepared by the free-radical polymerization of vinyl monomers, which were synthesized from low-cost raw materials through three high-yield synthesis steps. The combination of the flexible non-conjugated polyvinyl main chain and hole-transporting methoxydiphenylamine-substituted carbazole side chains endowed PVCz-OMeDAD with excellent film-forming ability, a suitable energy level, and high hole mobility. As a result, by using an ultra-thin (≈30 nm) PVCz-OMeDAD film as cost-effective dopant-free polymer HTM, the conventional n-i-p-type PSCs demonstrated a power conversion efficiency (PCE) up to 16.09 %, suggesting the great potential of the polymer film for future low-cost, large-scale, flexible PSCs applications.