The precise synthesis of Cu NCs is a highly desirable and controllable route for the preparation of desired structures and properties, which facilitates the rational design of valuable probes for fluorescence sensing and the understanding of structure-property relationships. Herein, an ion-exchange strategy combined with a bottom-up synthetic approach was utilized in the synthesis process of Cu NCs for the first time, which achieved the controllable synthesis of Cu NCs and in situ anchoring of Cu NCs on the support material HPU-14. The as-prepared Cu NCs@HPU-14-4h not only had a good peroxidase-like property but also exhibited stable dual-emitting fluorescence at 470 and 620 nm. Notably, the peroxidase-like property endowed Cu NCs@HPU-14-4h with the capability of highly sensitive colorimetric detection of H