Poled polymer films doped with novel nonlinear organic materials, α-cyano unsaturated carboxylic acid (α-CUCA) derivatives, are prepared. Linear and second-order nonlinear optical properties are investigated. It is found that as the value of hyperpolarizability of the derivatives increases, the second-order nonlinear susceptibility of the film increases. Cerenkov-type second harmonic generation (SHG) of Nd: YAG laser is realized in a poled polymer waveguide doped with the α-CUCA material with a slight absorption at doubled wavelength.