Liquid metals (LMs) are electronic liquid with enigmatic interfacial chemistry and physics. These features make them promising materials for driving chemical reactions on their surfaces for designing nanoarchitectonic systems. Herein, we showed the interfacial interaction between eutectic gallium-indium (EGaIn) liquid metal and graphene oxide (GO) for the reduction of both substrate-based and free-standing GO. NanoIR surface mapping indicated the successful removal of carbonyl groups. Based on the gained knowledge, a composite consisting of assembled reduced GO sheets on LM microdroplets (LM-rGO) was developed. The LM enforced Ga3+ coordination within the rGO assembly found to modify the electrochemical interface for selective dopamine sensing by separating the peaks of interfering biologicals. Subsequently, paper-based electrodes were developed and modified with the LM-rGO that presented the compatibility of the assembly with low-cost commercial technologies. The observed interfacial interaction, imparted by LM's interfaces, and electrochemical performance observed for LM-rGO will lead to effective functional materials and electrode modifiers.