To set up a sampling and analysis strategy for particulate matter (PM) based on the time periods used in international standards is often inadequate for assessing the impact of day/night cycles or episodic emissions on urban air quality. To obtain a detailed physico–chemical characterization of urban PM when concentrations exceed the regulatory thresholds, a new rotary cascade impactor named the Time-Resolved Atmospheric Particle Sampler (TRAPS) was designed and tested for coarse and fine particle sampling. The TRAPS implementation, coupled with Optical Particle Counter measurements, provides time-resolved samples that can be analyzed by a wide range of single-particle analysis techniques. The TRAPS theoretical design was verified experimentally. Experimental cut-off diameters of 1.32 and 0.13 µm, respectively, for coarse and fine stages, were found in good agreement with theoretical values. Additionally, good trace separation, preventing inter-sample contamination, was evidenced by Scanning Electron Microscopy (SEM). The homogeneous distribution of particles of different types over a trace was also verified. As a case study, automated SEM-EDX analysis of 2500 particles, collected during two pollution peaks of a transient PM2.5 pollution event, revealed that individual particles’ chemical composition was influenced by local sources during the first pollution peak, and mainly transported during the second peak.