A novel and sensitive approach for the accurate and precise determination of Pb in environmental samples is presented using transition metal ion-assisted photochemical vapor generation (PVG) for sample introduction with multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) detection. A significant improvement in PVG efficiency of lead is achieved in the presence of transition metal ions (Co(2+) and Ni(2+)) in solutions of 5% (v/v) formic acid. The determination of Pb in digests of sediment or soil samples is readily achieved due to coexisting transition metal ions which facilitate the PVG reaction. The method detection limit of 0.005 ng g(-1) (3σ) using external calibration is comparable to that obtained using hydride generation (HG) ICPMS. However, PVG methodology is simpler, results in lower blanks, and avoids unstable reagents. The accuracy of the proposed method was demonstrated by analysis of several environmental certified reference materials (CRMs; SLRS-5 and SRM1640a river water CRMs and MESS-3, MESS-4, and SRM2702 sediments) with satisfying results. High precision of determination (<0.4% RSD) of Pb in river water and sediments was realized on the basis of isotope dilution calibration.