Polysaccharide polyelectrolytes with tunable cross-linked structures and intrinsic conductivity and antibiosis address the energy consumption and high carbon emissions of wearable electronic devices. However, it is a great challenge to fabricate polysaccharide ionohydrogels with high conductivity and low stress loss for new energy generation and storage and other multiple occasion applications. Herein, a novel organogel polyelectrolyte (OST/P(AM-co-DMAEA-Q)/ZA) based on conjoined double cross-linked networks with high intrinsic conductivity, robust adhesion, and antibacterial properties is successfully prepared using oxidized starch (OST) and poly(ionic liquid) electrolyte (P(AM-co-DMAEA-Q)). The organogel polyelectrolyte exhibits 446% mechanical stretchability, 136 mS m−1 conductivity and 100% antibacterial efficacy against E. coli. A series of self-powered polyelectrolyte-based energy and sensing devices are constructed and the assembled triboelectric nanogenerators (TENGs) harvest performance with an open-circuit voltage of 118 V, while the supercapacitors (SCs) possess a high energy storage capacity of 87.84 mF cm−2 and long-term durability. Furthermore, the organogel polyelectrolyte demonstrates moisture-electric generation by utilizing ambient moisture to generate electricity. Additionally, the strain sensors effectively reproducibility detect human motions and serve as temperature sensors with a rapid response rate. This work develops a starch organogel polyelectrolyte for self-powered energy and sensing applications via the designed dual cross-linked networks.