Planar-structured HC(NH2 )2 PbI3 (FAPbI3 ) perovskite solar cells were prepared via a two-step deposition process. To investigate the role of interface, the perovskite morphology was intentionally modified by varying HC(NH2 )2 I concentration. Surface and grain sizes of the deposited FAPbI3 became rougher and larger as the HC(NH2 )2 I concentration decreased from 58.2 to 40.7 mM. Average photocurrent was improved but photovoltage deteriorated slightly with decreasing concentration. Consequently, the average efficiency was improved from 7.82 % to 10.70 % and the best efficiency of 12.17 % was obtained at 40.7 mM. Photoluminescence (PL) at TiO2 /FAPbI3 interface was reduced with decreasing concentration, which was, however, reversed at FAPbI3 /spiro-MeOTAD one. By correlating PL data and the photovoltaic performance, we concluded that the TiO2 /perovskite interface plays a crucial role in determining photocurrent while the perovskite/spiro-MeOTAD interface is important in governing photovoltage.