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A new immunoprobe, which can initiate the sedimentation of Ag nanoparticles (NPs) on an electrode surface, was developed for the electrochemical detection of carbohydrate antigen 72-4 (CA 72-4). To design the immunoprobe, zeolitic imidazolate frameworks (ZIFs) were employed as the carrier to enrich thionine molecules, then bovine serum albumin (BSA) was modified on the electrode surface. Advantageously, BSA, served as an anchor to further attach the labeling antibodies (Ab2) and alkaline phosphatase (ALP) to also be modified on the sur