Conductive　hydrogels　have　found　large　application　prospects　in　the　fabrication　of　flexible　multifunctional　electronic　devices　for　future-generation　wearable　human-machine　interactions.　However,　their　inferior　mechanical　strength,　low-temperature　resistance,　and　non-recyclability,　resulting　in　the　waste　of　resources,　severely　hinder　their　application.　Thus,　starch　bio-based　hydrogels　have　attracted　significant　attention.　Starch　is　the　most　abundantly　available　biodegradable　biopolymer.　However,　starch　bio-based　hydrogels　usually　show　low　toughness,　high　brittleness　and　low　anti-freezing　properties.　Thus,　to　address　these　issues,　herein,　glycerol　and　CaCl2were　concurrently　introduced　to　a　starch/poly(vinyl　alcohol)　(PVA)　hydrogel　to　improve　its　mechanical,　thermal　and　conductive　properties.　The　effect　of　glycerol　and　CaCl2on　the　crystallinity,　mechanical,　thermal　and　conductive　properties　was　revealed　by　X-ray　diffraction,　tensile　testing,　differential　scanning　calorimetry,　and　electrochemical　impedance　spectroscopy.　The　thermoplasticity　and　healing　properties　of　the　starch/PVA/glycerol/CaCl2organohydrogel　was　also　evaluated.　Due　to　the　role　of　glycerol　and　CaCl2,　the　compatibility　between　starch　and　PVA　improved,　and　thus　the　as-prepared　organohydrogels　showed　favorable　mechanical　flexibility　and　demonstrated　anti-freezing　ability　and　long-term　stability　at　ambient　temperature.　Besides,　the　abundant　hydrogen　bonds　formed　among　PVA,　starch,　glycerol　and　water　endowed　the　organohydrogels　with　high　stretchability　(＞790%)　and　good　thermoplasticity.　Finally,　based　on　the　starch/PVA/glycerol/CaCl2organohydrogel,　a　flexible　all-solid-state　supercapacitor　and　strain　sensor　were　assembled　and　their　performances　were　measured.　The　supercapacitor　displayed　an　areal　specific　capacitance　of　107.2　mF　cm−2at　1　mA　cm−2.　Moreover,　the　strain　sensor　demonstrated　high　sensitivity　(gauge　factor　of　3.422)　and　could　be　directly　attached　to　the　human　body　to　detect　motion.　©　The　Royal　Society　of　Chemistry　2021.