Nd-doped GdVO4(Nd:GdVO4) films with a-axis preferred orientation were fabricated on SiO2/Si substrate by pulsed-laser deposition. Fluorescences at around 1065.0 and 1342.5 nm, corresponding to 4F3/2→4I11/2 and 4F3/2→4I13/2 transitions, respectively, were excited simultaneously with an 808 nm diode laser. Waveguide behaviors in the film were investigated by using the prism coupling technique at the wavelength of 632.8 nm. Both TE and TM mode spectra revealed that favorable light confinements were achieved within the Nd:GdVO4 waveguide layer. Additionally, the optically anisotropic properties of the film were studied in detail.