In situ measurements of size-resolved aerosol chemical compositions and its optical properties were concurrently carried out at an urban site in mega-city Beijing from October 24 to November 9, 2007. The main objective was to quantitatively study the relationship between aerosol chemical compositions and its hygroscopic properties, to estimate the influence of relative humidity (RH) on aerosol scattering coefficient and to quantitatively investigate visibility impairment due to particle hygroscopic growth. The hygroscopic factor of aerosol scattering coefficient (f(RH)), which is defined as the ratio of aerosol scattering coefficient at wet condition to that at dry condition (RH ≤ 30%), was calculated with the measured aerosol optical properties at dry and ambient conditions. The relationship between f(RH) and RH was fitted by empirical equation and the fitting parameters were calculated. Meanwhile, f(RH) for externally mixed aerosols or internally mixed aerosols was modeled based on size segregated particulate chemical composition. The modeled f(RH) agreed well with the measured f(RH). Empirical formula for atmospheric visibility based on mass concentration of PM2.5 and f(RH) was proposed. The result of this study is not only proven that RH, in addition to the mass concentration of PM2.5, played an important role on visibility impairment, but also provide practical aid for air quality control to improve the visibility in the megacity region of Beijing.