Aerosol optical thickness (τaer) is a fundamental parameter for analyzing aerosol loading and associated radiative effects. The τaer can constrain many inversion algorithms using passive/active sensor measurements to retrieve other aerosol properties and/or the abundance of trace gases. In the next wave of spectroradiometric observations from geostationary platforms, we envision that a strategically distributed network of robust, well-calibrated ground-based spectroradiometers will comprehensively complement spaceborne measurements in spectral and temporal domains. Spectral τaer can be accurately obtained from direct-Sun measurements based on the Langley calibration method, which allows for the analysis of distinct spectral features of the calibration results. In this study, we present a spectral τaer retrieval algorithm for an in-house developed, ﬁeld deployable spectroradiometer instrument covering wavelengths from ultraviolet to near-infrared (UV-Vis-NIR). The spectral total optical thickness obtained from the Langley calibration method is partitioned into molecular and particulate components by utilizing a least squares method. The resulting high temporal-resolution τaer and Ångström Exponent can be used effectively for cloud screening. The new algorithm was applied to month-long measurements acquired from the rooftop at National Aeronautics and Space Administration Goddard Space Flight Center’s Building 33. The retrieved τaer demonstrated excellent agreement with those from well-calibrated Aerosol Robotic Network Sun photometers at all overlapping wavelengths (correlation coefﬁcients higher than 0.98). In addition, empirical stray light corrections considerably improved τaer retrievals at short wavelengths in the UV. The continuous spectrum of τaer from UV-Vis-NIR spectroradiometers is expected to provide more informative constraints for retrieval of additional aerosol properties such as refractive indices, size, and bulk vertical distribution.