Deposition of Langmuir-BIodgett, spectra and second order nonlinear optical properties of Asymmetric Substituted naphthalocyanine derivatives were investigated by using linear absorption and second harmonic generation (SHG) technique. The results showed that the substituent had a significant influence on the second order nonlinear optical properties of naphthalocyanine derivatives. The second order nonlinear optical susceptibility χ(2) of tri-tert-butyl-cyan naphthalocyanine was about 3.7×10^{-8} esu, which was 37 times more than that of tri-tert-butyl naphthalocyanine.