Surfactant-free ZCCPEs were formed via a facile approach.
Meso-scale ZCCPs with high surface charges were confirmed as effective Pickering emulsifiers.
Meso-scale hybrid interfacial architectures were visualized for the ZCCPEs.
Stable gels were obtained from the ZCCPEs by a facile one-step freeze-drying process.
ZCCPEs possessed high physical, chemical and microbial stability.