Functionalized nanofibrous membranes have been produced via electrospinning with a polymer solution of 19% (w/w) of nylon 66 prepared in a formic acid/chloroform mixture (75:25 v/v). The optimum parameters of electrospinning, like voltage, flow rate, tip and collector distances, were achieved and produced nanofiber membranes with a thickness of 287 nm. Then the nanofiber membranes were functionalized by (3-mercaptopropyl)trimethoxysilane (TMPTMS) at various amounts. Three different initial concentrations of metal ions and three different levels of pH were chosen. The effect of filtration process parameters such as the initial concentration of metal solution, pH of the solution, and the amount of functionalizer trimethoxysilane (TMPTMS) on the adsorption was studied. In surveying filtration process parameters, the results showed that metal ion rejection increased by increasing the pH of the solution and decreased by increasing the initial concentration of the effluent. By increasing the amount of functionalizer, removal efficiency increased. The results showed that the maximum efficiency of absorption of cadmium and nickel were 93.0 and 97.6%, respectively, and the filtering mechanism of the membrane is the blocking pores type. The adsorption data of cadmium and nickel ions fitted particularly well with the Freundlich isotherm.