A porous-microspheres Li–Si film (PMLSF) is prepared by multi-step constant current (MSCC) electrodeposition on Cu foil. Its structure and morphology are characterized using X-ray diffraction (XRD) and scanning electron microscope (SEM). As negative electrodes of lithium-ion batteries, the PMLSF electrode delivers the first gravimetric and geometric charge capacities of 2805.7mAhg−1 and 621.9μAhcm−2 at the current density of 25.5μAcm−2, and its initial coulombic efficiency is as high as 98.2%. When the PMLSF electrode is cycled in VC-containing electrolyte, the superior cycling performance can be obtained. After 50 cycles, 96.0% of its initial capacity is retained at the current density of 50.0μAcm−2. Electrochemical impedance spectra (EIS) research confirms the positive effect of VC additive on the behavior of the PMLSF electrode.