The radical intermediate, which is produced in the process of electroless nickel plating, was detected in the presence of water-soluble trap α-4-pyridy1-N-tert-buty1 nitrone(POBN) or α-phenyl-tert-buty1 nitrone(PBN) by electron spin resonance(ESR) spectroscopy. The results obtained indicated that a 16-line(g=2.006 1, aβC—H=1.98×10-4 T, aγP—H=3.32×10-4 T, aN=aP=15.93×10-4 T) or a 18-line (g=2.004 9, aβC—H=aγP—H=2.38×10-4 T, aP=17.72×10-4 T, aN=16.20×10-4 T) ESR spectrum was observed in the process of electroless nickel plating when spin trap PBN or POBN was added. The spectra-line patterns and hyperfine coupling parameters were greatly indentical with those in the solution composed of Ti3+(0.01 mol/L)+H2O2(0.05 mol/L)+H2PO-2(0.01 mol/L)+POBN or PBN(0.01 mol/L). Therefore, the spin adducts formed in the process of electroless nickel plating could be ascribed to the adducts belonging to HPO-·2 and POBN or PBN and it follows that the anion radical HPO-·2 was really produced from the oxidation of sodium hypophosphite in the process of electroless nickel plating.