Liquid metal (LM) composites are a class of emerging soft multifunctional materials that are promising for a variety of applications, yet the chemistry properties of LM have not been fully understood. Here, we report that LM nanoparticles can directly perform as a photoinitiator for radical polymerization and the in situ development of highly tough and multifunctional LM hydrogel composites. It is revealed that the photocatalytic activity of LM nanoparticles originates from the oxide layer on LM. Significantly, positively charged metal-organic framework (MOF) nanoparticles are used to stabilize LM nanoparticles in aqueous solutions, where the MOF can anchor on the surface of LM nanoparticles by electrostatic interaction while helping to preserve the unshielded oxide layer, therefore realizing the highly efficient photoinitiation and polymerization. The LM nanoparticle-initiated photopolymerization is shown to develop hydrogel composites featuring excellent stretchability, stimuli responsiveness, and sustained photocatalytic activity. The photocatalytic polymerization initiated by LM nanoparticles not only deepens the understanding on the semiconductor properties of the oxide skin on LM but also broadens the application scenarios of multifunctional LM/polymer composites in smart materials, wearable electronics, and soft robotics.