AbstractAqueous multiphase systems have attracted a lot of interest recently espeically due to target applications in the biomedical field, cosmetics, and food. In turn, water‐in‐water Pickering emulsions are investigated frequently. In here, graphitic carbon nitride (g‐CN) stabilized water‐in‐water Pickering emulsions are fabricated via the dextran and poly(ethylene glycol)‐based aqueous two‐phase system. Five different derivatives of g‐CN as the Pickering stabilizer are described and the effect of g‐CN concentration on droplet sizes is investigated. Stable emulsions (up to 16 weeks) are obtained that can be broken on purpose via various approaches, including dilution, surfactant addition, and most notably light irradiation. The novel approach of water‐in‐water emulsion stabilization via g‐CN opens up considerable advances in aqueous multiphase systems and may also introduce photocatalytic properties.