Complexation behavior of NpO2 + with ortho-silicic acid (o-SA) has been studied using solvent extraction at ionic strengths varying from 0.10 to 1.00M (NaClO4) at pcH 3.68±0.08 and 25 °C with bis-(2-ethylhexyl) phosphoric acid (HDEHP) as the extractant. The stability constant value (log β1) for the 1:1 complex, NpO2(OSi(OH)3), was found to decrease with increase in ionic strength of the aqueous phase [6.83±0.01 at I=0.10M to 6.51±0.02 at I = 1.00M]. These values have been fitted in the SIT model expression and compared with similar values of complexation of the metal ions Am3+, Eu3+, UO2 2+, PuO2 2+, Np4+, Ni2+ and Co2+. The speciation of NpO2 +-o-silicate/carbonate system has been calculated as a function of pcH under ground water conditions.