Electrochemiluminescence (ECL), as an advanced sensing process, can selectively control the generation of excited states by changing the potential. However, most of the existing ECL systems rely on poisonous coreactants to provide radicals for luminescence; although the ECL efficiency was improved, the athematic coreactants will cause unpredictable interference to the accurate analysis of trace targets. Herein, we realized the ECL of nonemitting molecules by performing intramolecular electron transfer in the olefin-linked covalent organic frameworks (COFs), with a high efficiency of 63.7%. Employing internal dissolved oxygen as the coreactant, it is well suitable for the analysis of various complex samples in the environment. Taking nuclear contamination analysis as the goal orientation, we further illustrated a design of a "turn-on" uranyl ion monitoring system integrating fast response, low detection limit, and high selectivity, showing that new ECL-COFs are promising to facilitate environment-related sensing analysis and structure-feature correlation mechanism exploration.