This work proposes a new perovskite solar cell structure by inserting a polymer interlayer between perovskite and hole transporting material (HTM) to minimize the interface losses via interface engineering. The multifunctional interlayers improve the photovoltaic efficiency and device stability by shielding perovskite from moisture, suppressing charge combination, and promoting hole transport. The five different polymer layers are utilized to investigate the relationships of polymer structure, layer morphology and cell performance systematically. It is found that a reliable power conversion efficiency exceeding 19.0% is realized based on P3HT/spiro-OMeTAD composite structure, surpassing that of pure spiro-OMeTAD (15.0%). Moreover, the device with P3HT interlayer shows more brilliant long-term stability than that without interlayer when exposed into moisture. The enhanced device performance based on P3HT interlayer compared with the other polymers can be ascribed to the long hydrophobic alkyl chains and the small molecule monomers of P3HT, which contribute to self-assembly of the polymers into insulating layers and formation of the efficient pi-pi stacking in polymer/spiro-OMeTAD interface simultaneously. This study provides a practical route for the integration of a new class of easily accessible, solution-processed interfacial polymer materials for high-performance and long-time stable PSC.