Porous poly(L-lactic acid) (PLLA) nanofibrous membrane with the high surface area was developed by electrospinning and post acetone treatment and used as a substrate for deposition of chitosan. Chitosan was coated onto porous nanofibrous membrane via direct immersion coating method. The porous PLLA/chitosan structure provided chitosan a high surface framework to fully and effectively adsorb heavy metal ions from water and showed higher and faster ion adsorption. The composite membrane was used to eliminate copper ions from aqueous solutions. Chitosan acts as an adsorbent due to the presence of aminic and hydroxide groups which are operating sites for the capture of copper ions. The maximum adsorption capacity of copper ions reached 111.66 ± 3.22 mg/g at pH (7), interaction time (10 min) and temperature (25 °C). The adsorption kinetics of copper ions was established and was well agreed with the second-order model and Langmuir isotherm. Finally, the thermodynamic parameters were studied.