On-skin electronics that simultaneously ensure biocompatibility and stable electrical operation on soft tissue is still challenging. This study introduces a dual-layered and natural material based nanofiber platform designed for multifunctional on-skin operation (from energy harvesting to transdermal drug delivery). The ultrathin electronic patch consists of polyaniline (PANI)-coated cellulose nanofibers and silk fibroin nanofibers. The top PANI/cellulose nanofiber layer, exhibiting the resistivity of 0.315 Ω·m and over 90 % light absorbance in full visible range, functions as a flexible electrode. The silk nanofiber layer offers the skin-compatibility and strong adhesion to biological tissues, along with the capability of drug-loading. The nanofiber mesh structure withstands mechanical deformation, including compression, stretching, and bending, while its porous nature enhances breathability and hygiene. The fully nanofiber-based electronic patch platform is flexible, adheres well to the skin, and conforms to curved surfaces. By integrating the conductive properties of PANI with the biocompatibility of silk fibroin, this dual-layered membrane enhances the efficacy of transdermal drug delivery while offering multifunctional capabilities such as energy harvesting in a triboelectric nanogenerator (TENG), programmable drug delivery, and thermal therapy. This innovative approach paves the way for advanced biomedical applications by combining multiple functionalities in a single platform.