For the practical applications of wearable electronic skin (e‐skin), the multifunctional, self‐powered, biodegradable, biocompatible, and breathable materials are needed to be assessed and tailored simultaneously. Integration of these features in flexible e‐skin is highly desirable; however, it is challenging to construct an e‐skin to meet the requirements of practical applications. Herein, a bio‐inspired multifunctional e‐skin with a multilayer nanostructure based on spider web and ant tentacle is constructed, which can collect biological energy through a triboelectric nanogenerator for the simultaneous detection of pressure, humidity, and temperature. Owing to the poly(vinyl alcohol)/poly(vinylidene fluoride) nanofibers spider web structure, internal bead‐chain structure, and the collagen aggregate nanofibers based positive friction material, e‐skin exhibits the highest pressure sensitivity (0.48 V kPa⁻¹) and high detection range (0–135 kPa). Synchronously, the nanofibers imitating the antennae of ants provide e‐skin with short response and recovery time (16 and 25 s, respectively) to a wide humidity range (25–85% RH). The e‐skin is demonstrated to exhibit temperature coefficient of resistance (TCR = 0.0075 °C⁻¹) in a range of the surrounding temperature (27–55 °C). Moreover, the natural collagen aggregate and the all‐nanofibers structure ensure the biodegradability, biocompatibility, and breathability of the e‐skin, showing great promise for practicability.