Herein, we develop direct current-generating triboelectric nanogenerators (DC-TENGs) based on the tribovoltaic p-n junction using n-type perovskite (CsFAMA) and p-type conductive polymer (PEDOT:PSS); CsFAMA based DC-TENG is shown to generate a high DC power output of about 2.1 µA cm−2 (current) and 0.33 V (voltage). We also introduce choline chloride (ChCl) to passivate the defects inside CsFAMA to improve the power-generating performance of DC-TENG by increasing triboelectric charge density, carrier mobility, and built-in potential, which are the key factors that determine device performance. Due to the synergetic effect of reduced defect sites (5.0×1015 cm−3 to 1.0×1015 cm−3), enhanced electron mobilities (1.0×10−2 cm2 V−1 s−1 to 2.3×10−2 cm2 V−1 S−1), and modulated work function, the passivated CsFAMA-based DC-TENG generates an output current density of 11 µA cm−2 and an output voltage of 0.80 V. Our results are expected to contribute to the development of high-performance DC-TENGs by presenting a promising strategy that involves controlling the triboelectric semiconducting interface.