Sum frequency generation (SFG) spectroscopic techniques are used to investigate the molecular orientation of adsorbed acetonitrile on rutile TiO2 (110) at the solid-vapor interface. Generally, most molecular orientation analyses using SFG have been performed on dielectric substrates, to avoid the spectral interference between resonant and the near-resonant background signal. Although rutile crystal can be treated as a dielectric substrate, its electronic state contributes to the intensity and interferes with the resonant signal when the SFG frequency is close to its band gap energy. In addition, the ruble crystal is a uniaxial birefringent material, and the (110) surface is anisotropic, which further complicates the spectral analysis. In this study, various SFG measurement techniques were applied, and quantitative analytical methods were established to interpret the surface orientation of an adsorbed molecule. SFG vibrational spectra of acetonitrile on rutile TiO2 (110) surface have been measured using distinct polarization combinations, polarization mapping, and null angle method. By varying the polarization combinations of SFG, the magnitude and shape of the spectra undergo substantial change, which originate from the interference between the near-resonant signal from the ruffle substrate and the resonance signal from the acetonitrile. Theory, simulation, and analytical methods for obtaining quantitative orientation information of a molecule on an anisotropic semiconductor substrate in the presence of a near-resonant signal are presented.