Aqueous two-phase systems (ATPSs) have primarily been developed in the form of emulsions to enhance their utilization in green and biocompatible applications. However, numerous challenges have arisen in forming stable and processable water-in-water (W/W) emulsion systems, as well as in fine-tuning the interconnectivity of their internal structure, which can significantly impact their performance. To effectively address these challenges, we elucidate, for the first time, the root cause of the poor stability of W/W emulsions. Leveraging this insight, we successfully stabilize W/W high internal phase emulsions (W/W HIPEs) characterized by an extremely thin continuous phase. This stabilization enables the fine-tuning of interconnectivity between dispersed droplets through photopolymerization of thin continuous phases, resulting in the fabrication of stable and processable all-aqueous gels. This W/W HIPE-based gel fabrication holds promise as a universal technology for a wide range of applications. It facilitates in situ polymerization of the continuous phase of W/W HIPEs, where target molecules are stored in the dispersed phase. Moreover, this method allows easy adjustment of the external release rate or internal transfer rate of target molecules by adjusting the interconnectivity of the internal structures.