A new self-powered brain-linked biosensing electronic-skin (e-skin) for detecting pH value and alcoholicity of beverages has been realized based on polydimethysiloxane/polypyrrole (PDMS/Ppy) nanostructures. This e-skin (linking brain and transmitting signal to the specific encephalic region) can work as an artificial gustation system for gustatory perception substitution without an external electricity source. The sensing units on the e-skin can efficiently convert mechanical energy (human motion) into triboelectric impulse. The triboelectric output can be influenced by pH value and alcohol concentration in common beverages (acidic, alkaline or alcoholic drinks), which can be treated as the bio-chemical sensing signal. The bio-chemical sensing behavior arises from the triboelectrification/bio-chemical-sensing coupling effect. The biosensing e-skin is simply linked to the brain of a mouse at the primary motor cortex area, and the inputting signal can take part in the mouse perception, thus realizing behavior interventions, e.g., shaking of legs. This study provides a novel approach for developing artificial gustation e-skin and self-powered brain-machine interaction system with low cost.