A pH-triggered transition from micellar aggregation to a host-guest complex was achieved based on the supramolecular interactions between calixpyridinium and pyrroloquinoline quinone disodium salt (PQQ-2Na) accompanied by a color change. Our design has the following three advantages: (1) a regular spherical micellar assembly is fabricated by the supramolecular interactions between calixpyridinium and PQQ-2Na at pH 6 in an aqueous solution, (2) increasing the pH can lead to a transition from micellar aggregation to a host-guest complex due to the deprotonation of calixpyridinium, and at the same time (3) increasing the pH can lead to a color change owing to the deprotonation of calixpyridinium and the complexation of deprotonated calixpyridinium with PQQ-2Na. Benefitting from the low toxicity of calixpyridinium and PQQ-2Na, this pH-induced transition from micellar aggregation to a host-guest complex was further studied as a controllable-release model.