The liquid-solid contact electrification mechanism has been explored in the aqueous solution system, but there are few systematic studies on oil-solid triboelectrification. Herein, an oil droplet triboelectric nanogenerator (Oil-droplet TENG) is designed as the probe to investigate the charge transfer properties at oil-solid interface. The charge transfer kinetics process is disclosed by the electrical signals produced, showing that the electron species initially predominated the oil-solid triboelectrification. The molecular structure and electronic properties of oil also affect triboelectric performance. Further, the charge transfer principle in multi-component liquid mixture during the electric double layer (EDL) development process is proposed to explain the component competition effect. As a proof of concept, a tubular-TENG is designed as a self-powered sensor for transformer oil trace water detection. The device demonstrates high water sensitivity with a detection limit of 10 mu L L-1 and a response range of 10-100 mu L L-1. This work not only reveals the oil-solid triboelectric and charge transfer competition mechanism in EDL, but also open up a new channel for real-time online monitoring of trace water in transformer oil, which holds promise for information perception and intelligent operation of transformers in the power industry.