Size‐fractionated aerosol particles were collected with a MOUDI 10‐stage cascade impactor from an urban roadside place in a downtown area of Hong Kong. Fine aerosol particulate samples from stage 6 (aerodynamic particle diameter between 0.56 and 1 μm) and stage 9 (aerodynamic particle diameter between 0.10 and 0.18 μm) were pretreated at a chosen temperature, including −100°C, −50°C, 25°C, and 60°C, in a load lock chamber and then analyzed using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) at the same temperature (−100°C). Principal component analysis (PCA) was applied to further analyze ToF‐SIMS spectra of aerosol particles with different pretreatment temperatures from two selected stages. ToF‐SIMS results showed that the intensities of aliphatic hydrocarbon ions such as C4H7+ and C4H9+ and amine ions such as C2H8N+ and C4H12N+ decreased with an increase of the pretreatment temperature under ultrahigh vacuum conditions. We have shown that analyses of this type of aerosol particles using ToF‐SIMS should not be conducted at ambient temperature but at low temperature (eg, −50°C). In addition, we also developed a procedure that can be used to analyze aerosol particle samples under ultrahigh vacuum environment.