Recently air pollution is seriously threatening the health of millions of people in China. The multiple sulfur isotopic composition of sulfate in PM2.5 samples collected in Beijing is used to better constrain potential sources and formation processes of sulfate aerosol. The Δ33S values of sulfate in PM2.5 show a pronounced seasonality with positive values in spring, summer and autumn and negative values in winter. Positive Δ33S anomalies are interpreted to result from SO2 photolysis with self-shielding, and may reflect air mass transport between the troposphere and the stratosphere. The negative Δ33S signature (-0.300‰ < Δ33S < 0‰) in winter is possibly related to incomplete combustion of coal in residential stoves during the heating season, implying that sulfur dioxide released from residential stoves in more rural areas is an important contributor to atmospheric sulfate. However, negative Δ33S anomalies (-0.664‰ < Δ33S ← 0.300‰) in winter and positive Δ33S anomalies (0.300‰ < Δ33S < 0.480‰) in spring, summer, and autumn suggest sulfur isotopic equilibrium on an annual time frame, which may provide an implication for the absence of mass-independent fractionation of sulfur isotopes (S-MIF) in younger sediments. Results obtained here reveal that reducing the usage of coal and improving the heating system in rural areas will be important for efficiently decreasing the emissions of sulfur in China and beyond.