For the first time, the poly(L-lactide acid) (PLLA) composites with C60 tetragonal single crystal (C60TSC) were fabricated through facile evaporation of the CHCl3 solution containing PLLA and C60. Results showed C60TSC in composites had side length in micron scale, and their mean size decreased, their number increased with C60 content in composites. The C60TSC in composites were face-centered cubic (fcc) lattice C60 single crystal composed of monomeric C60, and displayed blueshift relative to the UV absorption bands of C60. C60TSC formation resulted in PLLA composite with higher thermal stability, higher cold crystallization temperature as well as higher melting temperature than neat PLLA.