Electrochemiluminescence (ECL) has numerous merits such as high sensitivity and specificity for the detection applications on pharmacy, food safety, immunoassay, disease diagnosis, environmental monitoring, nucleic acid assay, and clinical treatment. However, the insufficiency of ECL luminescent reagents is restricting their adoption on complex systems or multi-analyte detections. In this work, to improve the selectivity and discrimination of ECL detection with one or less luminescent reagent, we employed multi-stopband photonic crystals (PCs) to enhance assigned ECL. The discrimination of ECL was well investigated to establish the quantitative description with PC stopbands. The multi-stopband PC electrode can facilely achieve 10 antibiotics qualitative and quantitative analysis with 100% accuracy and 0.44 μM LOD in PBS buffer and human serum. The selectivity of ECL detection for multi-analytes can be improved via designed PC luminescence amplifications. The exploration on PC selectivity for ECL enhancement will promote the realistic application of the ECL technique and contribute to the facile and efficient optical platform for clinical or health monitoring.