The high resolution accurate mass measurement of product ions formed by collisionally activated dissociation in an electrospray source has been achieved using a reversed-geometry double-focusing mass spectrometer and accelerating voltage scans. Accurate mass measurements of productions from angiotensin I, angiotensin II, leucine enkephalinamide, substance P (1-9) and a synthetic compound of pharmaceutical interest were obtained with an average error of <5 ppm.