To address the escalating power consumption of processors in data centers and the growing emphasis on environmental sustainability, the prospective shift from traditional air-cooling to immersion liquid cooling necessitates multiple functional integrations in polymer-based thermal conductive materials. Here, drawing inspiration from mussels, we showed a copolymer, poly(dimethylsiloxane-co-dopamine methacrylate) (PDMS-DMA), with a variety of reversible molecular interactions and simply combined with liquid metal (EGaIn) can yield a flexible, waterproof, and electrically insulating thermal conductive composite. The obtained PDMS-DMA/EGaIn composites demonstrate a harmonious blend of attributes, including a low modulus (75.8 kPa), high thermal conductivity of 6.9 W m-1 K-1, and rapid room-temperature self-healing capabilities, capable of complete repair within 20 min, even under water. Based on its electrically insulating and water resistance properties, PDMS-DMA/EGaIn emerges as a promising candidate for efficient and stable heat transfer in both air and underwater thermal management. Consequently, this water-resistant polymer-based composite holds significance for application in thermal protective layers for future immersion liquid cooling systems.