Distinct contrast of air quality and visibility before and during the 2008 Beijing Olympic Games provides a rare opportunity to investigate the links between PM2.5 mass, chemical composition, and light extinction in this megacity. Twenty-four hour integrated PM2.5 samples were collected, and light scattering coefficients and the concentrations of black carbon were measured at urban Beijing for this purpose during a measurement campaign from 1 July to 20 September 2008, which was classed into four stages according to the levels of emission control measures. Daily PM2.5 concentrations ranged from 15.9 to 156.7 µg m−3 with an average of 66.0 ± 35.1 µg m−3. The average PM2.5 mass during the Olympics decreased by 49% from the second stage (20 July to 7 August), mainly due to the reduction of secondary inorganic aerosols (i.e., sulfate, nitrate, and ammonium (SNA)). The counterintuitive increase of PM2.5 mass (by 27% on average) during the second stage with two most serious haze episodes, although more rigorous emission control measures were in place, compared to the first stage (1–19 July), was mainly explained by the unfavorable meteorology and input of sulfate aerosols. A daily PM2.5 mass threshold of 50 µg m−3 was extracted for frequent haze occurrence. The extinction fractions of SNA and organic material were each approximately 30% during the 20% best visibility days but changed to 81.7% and 8.4%, respectively, during the 20% worst visibility days. The results indicated that the role of SNA was magnified in haze formation during the 2008 summer in Beijing.