We demonstrate three-dimensional vibrational imaging of director structures in liquid crystals using coherent anti-Stokes Raman scattering (CARS) polarized microscopy. Spatial mapping of the structures is based on sensitivity of a polarized CARS signal to orientation of anisotropic molecules in liquid crystals. As an example, we study structures in a smectic material and demonstrate that single-scan CARS and two-photon fluorescence images of molecular orientation patterns are consistent with each other and with the structure model. Long-range orientational order is an important property of liquid crystals (LCs) [1]. Local average molecular orientations are described by the director n n− ≡ , which is an optical axis in the uniaxial LC materials. Non-invasive imaging of the three-dimensional (3-D) spatial patterns of ) ( r n r is important for fundamental LC research and for a broad range of technological applications. Fluorescence Confocal Polarizing Microscopy (FCPM) [2] visualizes 3-D director fields by taking advantage of (a) doping anisometric dyes that homogeneously distribute and align in the LC and (b) polarized excitation and fluorescence detection. In this approach, the absorption/emission transition dipoles of elongated dye molecules follow ) ( r n r and the polarized confocal imaging visualizes the 3-D director patterns [2]. However, this approach requires doping a specially selected dye that at small concentrations would provide strong contrast without affecting the LC properties. The labeling-free technique of interest is confocal Raman microscopy [3,4], which utilizes a Raman vibration and the signal dependence on orientations of molecular bonds. To study 3-D molecular orientation patterns, several techniques employ nonlinear processes, such as second harmonic generation (SHG) [5], third harmonic generation (THG) [6], and two-photon fluorescence (TPF) [7]. Coherent anti-Stokes Raman scattering (CARS) microscopy has been used for visualizing chemical composition in biological and lyotropic systems [8,9]. We report 3-D imaging of LC director structures using CARS polarized microscopy (CARSPM), which does not require doping the LC with dyes and offers chemical selectivity and bond-orientation specificity superior to that of other techniques [2][3][4][5][6][7]; it also provides 5 10 times faster imaging (stronger signal) than confocal Raman microscopy [3,4]. We demonstrate that CARSPM is a viable technique for mapping of 3-D patterns of molecular orientations and LC director dynamics.In CARS microscopy, a pump wave is used as a probe and the signal is derived by the 3-rd order nonlinear polarization