The Atmosphere-surface Radiation Automatic Instrument (ASRAI) is a newly developed hyper-spectral apparatus by Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences (AIOFM, CAS), measuring total spectral irradiance, diffuse spectral irradiance of atmosphere and reflected radiance of the land surface for the purpose of in-situ calibration. The instrument applies VIS-SWIR spectrum (0.4~1.0 μm) with an averaged spectral resolution of 0.004 μm. The goal of this paper is to describe a method of deriving both aerosol optical depth (AOD) and aerosol modes from irradiance measurements under free cloudy conditions. The total columnar amounts of water vapor and oxygen are first inferred from solar transmitted irradiance at strong absorption wavelength. The AOD together with total columnar amounts of ozone and nitrogen dioxide are determined by a nonlinear least distance fitting method. Moreover, it is able to infer aerosol modes from the spectral dependency of AOD because different aerosol modes have their inherent spectral extinction characteristics. With assumption that the real aerosol is an idea of “external mixing” of four basic components, dust-like, water-soluble, oceanic and soot, the percentage of volume concentration of each component can be retrieved. A spectrum matching technology based on Euclidean-distance method is adopted to find the most approximate combination of components. The volume concentration ratios of four basic components are in accordance with our prior knowledge of regional aerosol climatology. Another advantage is that the retrievals would facilitate the TOA simulation when applying 6S model for satellite calibration.