Using the single beam Z-scan technique with 38 ps pulse at 1.064 μm, self-defocusing was observed, and the nonlinear refractive index n2 and the real part of χ(3) for octa-PdPc-doped organically modified sol-gels were measured to be 1.1×10-12 esu and 1.6×10-13 esu, respectively. The third-order optical nonlinearity of octa-PdPc-doped organically modified sol-gels is one order of magnitude larger than that of organically modified sol-gel matrix.