A binder-free anode for lithium ion batteries consisting of micro-sized silicon particles and polyacrylonitrile (PAN) was prepared. By optimizing the size of the Si particles and the ratio of Si particles to PAN, the performance of the anode was greatly enhanced. Although its columbic efficiency in the first cycle is comparatively lower than that made by traditional methods, it increases to 99% in the 8th cycle, and remains above 99.5% for up to 190+ cycles. Due to its adhesivity and conductance, pyrolyzed PAN (PPAN) can be used both as a binder and the conductive agent at the same time.