A porous structured Si-based alloy comprising Ni, Al, Ti (Si-NAT alloy) was successfully prepared using the melt-spinning technique followed by acid treatment. The morphology and surface area of the porous Si-NAT alloy was evaluated by scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) method. As prepared porous Si-NAT alloy has 15 times larger surface area, compared to the rigid sample (untreated). Improved electronic conductivity of the Si-NAT alloy was enabled due to the formation of inactive matrix along with the porous structure, which buffer the stress repeatedly generated by the volume changes during the lithiation/delithiation process. The porous Si-NAT alloy shows stable cycle performance over 30 cycles without severe capacity degradation. A galvanostatic intermittent titration technique (GITT) and single-particle measurement provided the detailed insight into the internal properties of the porous Si-NAT alloy.