Silicon nanoparticles (Si NPs) were simply mixed with carbon nanofibers (CNFs) without any chemical process at various weight ratios, and the electrochemical properties of these nanoparticles as anode materials were investigated in lithium-ion batteries (LIBs). To study the effects of the physical incorporation of CNFs on the volumetric variations in Si NPs, the dilations of full cells were measured. The measured volumetric change of the anode using a mixture of Si NPs and CNFs was smaller than that calculated from the theoretical volumetric changes of Si and graphite. Although the reversible capacity of Si NPs faded sharply, the fading was mitigated by increasing the mixing ratio of CNFs. In particular, the Si NP/CNF mixture prepared at weight ratio retained a reversible capacity of >800 mAh/g with a capacity retention of 53.2% even after 100 cycles. CNFs alleviated stress and strain during the charge–discharge process even though there was no tight chemical bonding with Si NPs.