Perylene and its derivatives are often used in many analytical fields, but its electrochemiluminescence (ECL) behavior has been rarely reported. Here, a novel anodic ECL of 3,4,9,10-perylenetetracarboxylic acid (PTCA)/oxamic hydrazide (OHZ) has been investigated for the first time with OHZ as the coreactant. The mechanism of the PTCA/OHZ ECL system is discussed. This ECL system enables the detection of OHZ with a linear range from 0.0626 to 312.5 μM and a detection limit of 21 nM (S/N = 3). Moreover, a highly sensitive method for tannic acid determination has been developed based on the effective quenching of PTCA/OHZ ECL by tannic acid. The proposed method shows a linear range of 0.05–320 μM with the limit of detection at 5 nM for tannic acid (S/N = 3). This study indicates that PTCA/OHZ shows great potential for application in ECL analysis as a new low-cost ECL system.