Thiol-functionalized poly (acrylic acid)/SiO2 (PAA/SiO2) composite nanofiber membranes have been fabricated by a sol-gel electrospinning method and their adsorption capacity for Ag+, Cu2+ was investigated. Results showed the PAA/SiO2 fibers had a diameter between 300 nm-700 nm. FTIR results demonstrated that the mercapto groups have been introduced into the silica skeleton. The adsorption of Ag+, Cu2+ on the membranes fit the Redlich-Peterson isotherm model best. The equilibrium adsorption capacity of Ag+ (575.64 mg/g) on PAA/SiO2 nanofiber membranes is higher than Cu2+ (331.52 mg/g). The desorption rate reached 98% in 30 min. The removal rate of Ag+, Cu2+ still maintained above 75% after six regeneration cycles. Adsorption kinetics of Ag+, Cu2+ followed a pseudo-second-order model.