Quantitative measurement of polychlorinated biphenyl (PCB) isomers by response factor calibration (RFC) is evaluated with gas chromatography and the Hall electrolytic conductivity detector. The procedure requires neither isomer identification nor reference compounds identical to each measured PCB isomer. Weight percent chlorine is determined for five Aroclor mixtures by RFC and compared within a few percent of expected values. Individual PCB isomers are measured and quantitatively compared for Aroclor mixtures. Also, RFC determinations for ten PCB isomers contained in a test material reference solution are compared to the supplier's stated concentrations. These RFC measurements provide quantitative analyses in the absence of a standard for each measured component.