To address the issues of low sensitivity in the infrared detection of zero-value insulators on distribution lines and the lack of live-line detection methods, this paper, based on the luminescence mechanism of electroluminescent materials, develops a ZnS:Cu electroluminescent coating sprayed onto the junction between the insulator steel foot and cement. Subsequently, based on electric field and potential distribution simulation results as well as live-line test results, a self-recognition detection scheme for zero-value insulators in 35 kV distribution lines is proposed. The research results show that the voltage values calculated by the simulation for the insulators are inversely proportional to the voltage values required for insulator activation in the live-line tests. Under normal operating conditions, the electroluminescent coating on each insulator in the string emits light. The larger the electric field on the insulator surface, the greater the luminescence brightness grayscale value of the electroluminescent coating. However, the surface electroluminescent coating of zero-value insulators does not emit light. The research findings of this paper can effectively enhance the level of intelligence and work efficiency in detecting zero-value porcelain insulators on distribution lines.