Frozen complex coacervate core micelles (C3Ms) were developed as a class of particle stabilizers for Pickering emulsions. The C3Ms are composed of a core of electrostatically interacting weak polyelectrolytes, poly(acrylic acid) (pAA) and poly(dimethylaminopropylacrylamide) (pDMAPAA), surrounded by a corona of water-soluble and surface active poly(N-isopropylacrylamide) (pNiPAM). Mixing parameters of the two polymer solutions, including pH, mixing method, charge ratio, and salinity of the medium, were carefully controlled, leading to monodisperse, colloidally stable C3Ms. A combination of dynamic light scattering and proton nuclear magnetic resonance experiments showed that the C3Ms gradually disassembled from a dynamically frozen core state in pure water into free polyelectrolyte chains above 0.8 M NaCl. Upon formulation of dodecane-in-water emulsions, the frozen C3Ms adsorb as particles at the droplet interfaces in striking contrast with most of the conventional micelles made of amphiphilic block copolymers which fall apart at the interface. Eventually, increasing the salt concentration of the system triggered disassembly of the C3Ms, which led to emulsion destabilization.