Bi3+-complex ion is presented here as a less toxic stabilizer for use in electroless nickel plating (ENP) to replace the existing Pb2+ ion stabilizer. The asymmetric derivatives of EDTA are identified to be a type of coordination ligands that can combine with Bi3+ ions to form soluble complexes in the acidic ENP solution. In the ENP System studied the Bi3+-complex ion displays a critical stabilizer concentration of about 10(-5) mol/L, that is, the percolation concentration over which the ENP rate drops sharply. Besides the experimental measurement, deposition rates of both Ni and P are also simulated by using a kinetic model that has been derived from the double electric layer theory. The Bi3+-complex ion, behaving like conventional Pb2+ ion, stabilizes ENP bath through the chemical replacement reaction at the surface of Ni deposition layer and results in a passive plating surface. This investigation also verifies the properties of the EN deposit, which are insignificantly affected by the length of service time of the plating solution by employing Bi3+-complex ion stabilizer. (C) 2009 American Institute of Chemical Engineers AIChE J, 55: 1046-1055, 2009