The elimination of the electron transport layer (ETL) to fabricate ETL-free perovskite solar cells (PSCs) could save manufacturing cost and time. However, the direct contact of the perovskite and transparent conducting oxide (TCO) electrodes results in mismatched energy level alignment and current leakage. Therefore, ETL-free PSCs suffer from unsatisfactory photovoltaic performance. Herein, a special perovskite material with a cascaded band gap, called gradient homojunction perovskite (GHJP), is designed and synthesized by a large cation-assisted method. The inherent nature of GHJP was the type-II cascaded energy level alignment, which could block holes during the electron collection. This facilitated the dissociation of the excitons in the GHJP. Due to the excellent properties, ETL-free PSCs based on GHJP obtained 20.55% PCE, which was over 90% higher than that of ETL-free PSCs based on the control perovskite material.