Since 2015, research on liquid–solid triboelectric nanogenerators (L-S TENGs) has shown steady growth, with the primary focus on application domains such as engineering, physics, materials science, and chemistry. These applications have underscored the significant attention L-S TENGs have garnered in areas like human–nature interaction, energy harvesting, data sensing, and enhancing living conditions. Presently, doping composite dielectric materials and surface modification techniques are the predominant methods for improving the power generation capacity of TENGs, particularly L-S TENGs. However, studies exploring the combined effects of these two approaches to enhance the power generation capacity of TENGs remain relatively scarce. Following a review of existing literature on the use of composite material doping and surface modification to improve the power generation performance of L-S TENGs, this paper proposes an experimental framework termed “self-assembled surface TENG@carbonyl iron particle doping (SAS-TENG@CIP)” to investigate the integrated power generation effects of L-S TENGs when combining these two methods. Research cases and data results indicate that, for TENGs exhibiting capacitor-like properties, the enhancement of power generation performance through composite material doping and superhydrophobic surface modification is not limitless. Each process possesses its own inherent threshold. When these thresholds are surpassed, the percolation of current induced by material doping and electrostatic breakdown (EB) triggered by surface modification can lead to a notable decline in the power output capacity of L-S TENGs. Consequently, in practical applications moving forward, fully realizing the synergistic potential of these methods necessitates a profound understanding of the underlying scientific mechanisms. The conclusions and insights presented in this paper may facilitate their complex integration and contribute to enhancing power generation efficiency in future research.