Two new electron-rich molecules, 2,3,4,5-tetra[4,4'-bis(methoxyphenyl)aminophen-4 ''-yl]-thiophene (H111) and 4,4',5,5'-tetra[4,4'-bis(methoxyphenyl) aminophen-4 ''-yl]-2,2'-bithiophene (H112), which contain thiophene cores with arylamine side groups, are reported. When used as the hole-transporting material (HTM) in perovskite-based solar cell devices, power conversion efficiencies of up to 15.4% under AM 1.5G solar simulation were obtained. This is the highest efficiency achieved with HTMs not composed of 2,2',7,7'-tetrakis(N,N'-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD) and its isomers. Both HTMs, especially H111, have great potential to replace expensive spiro-OMeTAD given their much simpler and less expensive syntheses.