COP is the ratio between the cold produced and the energy spent. In terms of energy you can calculate the cooling energy produced (for example, if the thermoelectric element is used to cool a water flow, you can measure the heat absorbed from water in a certain span of time) and divide it for the electric energy used to feed the thermoelectric element in the same time span (Voltage * Current * time). The evaluation of COP for such components is easier than other classes of cooler/chiller (because of simplicity in electric energy measurement).
Astrain, David, A. Merino, L. Catalán, P. Aranguren, Miguel Araiz, D. Sánchez, R. Cabello, and Rodrigo Llopis. "Improvements in the cooling capacity and the COP of a transcritical CO2 refrigeration plant operating with a thermoelectric subcooling system." Applied Thermal Engineering 155 (2019): 110-122.