3,3' -Dioxo-1,1' (3H,3' H)spirobi[isobenzofuran]-5,6,5' ,6' -tetracarboxylic acid 1 was resolved successfully and the corresponding optically active polyimides PI were synthesized. The properties of the optically active PI and the racemic one were investigated. The results showed that the specific rotation of (-)-PI was about two times to that of the (+)-PI, and the regularity of the optically active PI was higher than that of the racemic one.