We propose a polarized, angle-resolved spectral (PARS) reflectometry for simultaneous thickness and refractive-index measurement of ultra-thin films in real time. This technology acquires a two-dimensional, angle-resolved spectrum through a dual-angle analyzer in a single shot by radially filtering the back-focal-plane image of a high-NA objective for dispersion analysis. Thus, film parameters, including thickness and refractive indices, are precisely fitted from the hyper-spectrum in angular and wavelength domains. Through a high-accuracy spectral calibration, a primary PARS system was built. Its accuracy was carefully verified by testing a set of SiO2 thin films of thicknesses within two µm grown on monocrystalline-Si substrates against a commercial spectroscopic ellipsometer. Results show that the single-shot PARS reflectometry results in a root-mean-square absolute accuracy error of ∼1 nm in film thickness measurement without knowing its refractive indices.