Molecularly engineered novel dopant-free hole-transporting materials for perovskite solar cells (PSCs) combined with mixed-perovskite (FAPbI(3))(0.85)(MAPbBr(3))(0.15) (MA: CH3NH3+, FA: NH=CHNH3+) that exhibit an excellent power conversion efficiency of 18.9% under AM 1.5 conditions are investigated. The mobilities of FA-CN, and TPA-CN are determined to be 1.2 x 10(-4) cm(2) V-1 s(-1) and 1.1 x 10(-4) cm(2) V-1 s(-1), respectively. Exceptional stability up to 500 h is measured with the PSC based on FA-CN. Additionally, it is found that the maximum power output collected after 1300 h remained 65% of its initial value. This opens up new avenue for efficient and stable PSCs exploring new materials as alternatives to Spiro-OMeTAD.