The electrochemical performance of a composite of nano-Si powder and a pyrolytic carbon of polyvinyl chloride (PVC) with carbon nanofiber (CNF) was examined as an anode for solid-polymer lithium-ion batteries. Nano-Si powder was firstly coated with carbon by pyrolysis of PVC and then mixed with CNF (referred to as Si/C@CNF) using a rotation mixer. The composite exhibited good cycling performance, but suffered from a large irreversible capacity loss of which the retention was less than 60%. In order to reduce the loss, a thin lithium sheet was attached to the Si/C@CNF electrode surface as a reducing agent. The irreversible capacity of the first cycle was lowered to as much as 0mAhg−1 and after the third cycle, the lithium insertion and extraction efficiency was almost 100%. A reversible capacity of more than 1000mAhg−1 was still maintained after 40 cycles.