An intelligent drug delivery nanosystem has been developed based on biodegradable supramolecular polymer micelles (SMPMs). The drug release can be triggered from SMPMs responsively by a bioactive agent, L ‐phenylalanine in a controlled fashion. The SMPMs are constructed from ethylcellulose‐graft‐poly(ε‐caprolactone) (EC‐g‐PCL) and α‐cyclodextrin (α‐CD) derivate via host–guest and hydrophobic interactions. It has been found that these SMPMs have disassembled rapidly in response to an additional L ‐phenylalanine, due to great affinity discrepancy to α‐CD between L ‐phenylalanine and PCL. Experiments have been carried out on trigger‐controlled in vitro drug release of the SMPMs loaded with a model porphyrin based photosensitizer THPP. The result shows that the SMPMs released over 85% THPP in 6 h, which is two orders magnitudes faster than that of control. Also investigated is the photodynamic therapy (PDT) of THPP‐loaded SMPMs with and without L ‐phenylalanine on MCF‐7 carcinoma cell line. An effective trigger‐concentration dependent lethal effect has been found showing promise in clinical photodynamic therapy.