We studied linear and nonlinear optical properties of four different phthalocyanines: vanadyl and copper phthalocyanines substituted with chiral branched side chains, (S)(OMeBu)8VOPc, (S)(OMeBu)8CuPc; a racemic analogue (R,S)(OMeBu)8VOPc; vanadyl phthalocyanine substituted with linear side chains, (OBu)8VOPc. We investigate the molecule packing and their third-order nonlinear optical response in terms of chirality, planarity, and side chain structures. Molecular arrangement of (S)(OMeBu)8VOPc in the thin films was determined to be a columnar phase with rectangular 2D crystals by X-ray diffraction studies. The thin films of (S)(OMeBu)8VOPc diplayed CD activity. While, a chloroform solution of this compound did not show any CD. Therefore, we conclude that the CD in the films must result from the chiral aggregation of the molecules. The Χ(3) value of the flims of (S)(OMeBu)8VOPc was determined for 6.7×10-11 esu by third harmonic generation at 1.907 μm and this value was larger than those of (R,S)(OMeBu)8VOPc, (R,S)(OMeBu)8CuPc, and (OBu)8VOPc.