The problem of industrial wastewater containing heavy metals is always a big concern, especially Cu2+, which interprets the soil activity in farmland and leaves a negative impact on the environment by damaging the health of animals. Various methods have been proposed as countermeasures against heavy-metal contaminations, and, as a part of this, an electrospun nanofibrous adsorption method for wastewater treatment is presented as an alternative. Poly(lactic acid) (PLA) is a biopolymer with an intrinsic hydrophobic property that has been considered one of the sustainable nanofibrous adsorbents for carrying adsorbate. Due to the hydrophobic nature of PLA, it is difficult to adsorb Cu2+ contained in wastewater. In this study, the hydrophilic PLA/poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) (PEG-PPG-PEG) nanofibrous adsorbents with different silicon dioxide (SiO2) concentrations were successfully prepared by electrospinning. A hydrophilic group of PEG-PPG-PEG was imparted in PLA by the blending method. The prepared PLA/PEG-PPG-PEG/SiO2 nanofibrous adsorbents were analyzed with their morphological, contact angle analysis, and chemical structure. The Cu2+ adsorption capacities of the different PLA/PEG-PPG-PEG/SiO2 nanofibrous adsorbents were also investigated. The adsorption results indicated that the Cu2+ removal capacity of PLA/PEG-PPG-PEG/SiO2 nanofibrous adsorbents was higher than that of pure ones. Additionally, as an affinity nanofibrous adsorbent, its adsorption capacity was maintained after multiple recycling processes (desorption and re-adsorption). It is expected to be a promising nanofibrous adsorbents that will adsorb Cu2+ for wastewater treatment.