Highly soluble asymmetrically substituted vanadylphthalocyanines with dodecakis(2,2,2-trifluoroethoxy) groups as a donor and a mono-nitro group as an acceptor substituent, or with extended exocyclic conjugation, have been synthesized and characterized. Their linear and nonlinear optical properties were studied. Second harmonic generation of thin films of poly(methyl methacrylate) doped with these vanadylphthalocyanines was observed after electric poling at a fundamental wavelength of 1.064 mu m.