Water-in-water (W/W) emulsions are of interest for various applications due to their inherent biocompatibility, ultralow interfacial tensions, and large interface thickness. However, it is still challenging to prepare stable W/W emulsions with tailored phase architectures compared to oil-in-water (O/W) and water-in-oil (W/O) emulsions. Here, we report a multilayer-stabilized W/W emulsion composed of poly(ethylene glycol)/dextran in the presence of DNA strands. The W/W emulsions present onion-ring-like structures, which are interpreted by a nanofluid film model. Emulsion behavior, e.g., stability, interface tension, etc., can be controlled by the type of DNA (single or double strands), DNA concentration, and volume fraction of dispersed phase. Our findings could broaden the preparation of novel emulsions for potential applications in emulsion polymerization, new media of homogeneous catalysis, and DNA transportation of water-in-water media.