The electrochemical performance of the sulfurized polyacrylonitrile (SPAN)/Li cell affected by the Li2SiO3 particles that added between cathode and separator in the assembly process is studied. Fast capacity decay happens to the base SPAN/Li cell without Li2SiO3 due to deactivation of sulfur and side reactions etc.. However, the decay is obviously mitigated in the presence of Li2SiO3. Reversible capacity retention of 79% can be achieved after 100 cycles at 0.5C, while it is less than 10% for its counterpart. XPS and TEM measurements are conducted and the result indicates a positive effect of Li2SiO3 on the inhibition of side reactions, because Li2SiO3 can hold the dissociated sulfur substances and consume PF5/HF in the carbonate electrolyte.