High-performance flexible sensors capable of direct integration with biological tissues are essential for personalized health monitoring, assistive rehabilitation, and human–machine interaction. However, conventional devices face significant challenges in achieving conformal integration with biological surfaces, along with sufficient biomechanical compatibility and biocompatibility. This research presents an in situ 3D biomanufacturing strategy utilizing Direct Ink Writing (DIW) technology to fabricate functional bioelectronic interfaces directly onto human skin, based on a novel annealing PEDOT:PSS/PVA composite bio-ink. Central to this strategy is the utilization of a novel annealing PEDOT:PSS/PVA composite material, subjected to specialized processing involving freeze-drying and subsequent thermal annealing, which is then formulated into a DIW ink exhibiting excellent printability. Owing to the enhanced network structure resulting from this unique fabrication process, films derived from this composite material exhibit favorable electrical conductivity (ca. 6 S/m in the dry state and 2 S/m when swollen) and excellent mechanical stretchability (maximum strain reaching 170%). The material also demonstrates good adhesion to biological interfaces and high-fidelity printability. Devices fabricated using this material achieved good conformal integration onto a finger joint and demonstrated strain-sensitive, repeatable responses during joint flexion and extension, capable of effectively transducing local strain into real-time electrical resistance signals. This study validates the feasibility of using the DIW biomanufacturing technique with this novel material for the direct on-body fabrication of functional sensors. It offers new material and manufacturing paradigms for developing highly customized and seamlessly integrated bioelectronic devices.