SiO2-MgO hybrid fibers (SMHFs) were fabricated by one-step electrospinning process, characterized, and evaluated in heavy metal adsorption, for the first time. High-pressure steam (HPS) pretreated SMHFs showed high specific surface area (SBET) and large number of surface basic sites accompanied by the crystallization of MgO. The SMHFs showed high affinities for Pb(II) and Cu(II) with the distribution coefficients K-d > 100 L.g(-1) (when pH > 4). Langmuir model and pseudo-second-order kinetic model described the experimental data well, and the maximum adsorption capacities of 787.9 and 493.0 mg.g(-1) for Pb(II) and Cu(II) at 298 K were the highest among those of reported SiO2-MgO adsorbents. Thermodynamics indicated SMHFs had the spontaneous and physicochemical adsorption nature. SMHFs kept good capacities in the presence of interfering substances and retained their reusability. The SMHFs with the superiority of high efficiency, low cost, easy preparation and environmentally benign, have promising applications in wastewater treatment and relative fields.