The inorganic semiconductor is an attractive material in sewage disposal and solar power generation. The main challenges associated with environment‐sensitive semiconductors are structural degradation and deactivation caused by the unfavorable environment. Here, inspired by the pomegranate, a self‐protection strategy based on the self‐assembly of silver chloride (AgCl) particles is reported. The distributed photosensitive AgCl particles can be encapsulated by themselves through mixing aqueous silver nitrate and protic ionic liquids (PILs). A probable assembling mechanism is proposed based on the electrostatic potential investigation of PILs cations. The AgCl particles inside the shell maintain their morphology and structure well after 6 months light‐treatment. Moreover, they exhibit excellent photocatalytic activity, same as newly prepared AgCl particles, for degradation of methyl orange (MO), neutral red (NR), bromocresol green (BG), rhodamine B (RhB), Congo red (CR), and crystal violet (CV).