In the present study, the electrochemiluminescence (ECL) properties of Gd(OH)3 nanocrystals with K2S2O8 as the cathode coreactant were studied for the first time. Based on the prominent ECL behavior of this material and the excellent specificity of the aptamer technique, an ECL aptasensor for the detection of ochratoxin A (OTA) was formulated successfully. Over an OTA concentration range of 0.01 pg mL−1 to 10 ng mL−1, the change in the ECL signal was highly linear with the OTA concentration, and the limit of detection (LOD) was 0.0027 pg mL−1. Finally, the ECL aptasensor was further used to detect OTA in real samples (grapes and corn) and satisfactory results were obtained, which indicated that the built method is expected to be applied in food detection.