Calibration mixtures containing Ni-0 and V4+ in the range from 500 to 4000 ppm have been prepared using various supports (silica, alumina, titania and ultrastable Y zeolite (USY)) with different particle sizes. ESR measurements revealed a linear relation between the impregnated metal amounts and the registered ESR signal integrals and/or intensities, suitable for the determination of the NiO (reduced to Ni-0) and V4+ contents in FCC catalysts, respectively. The amount of NiO in a FCC equilibrium catalyst was determined to about 1300 ppm of a total of 2500 ppm Ni compound present in this sample, whereas the amount of V4+ was estimated to about 1800 ppm of a total of 2800 ppm vanadium species. Hence, this catalyst contains about 1000 ppm V5+.