The particle emissions from a commercial brake system utilizing copper-free pads have been characterized on a brake dynamometer under two real-world driving cycles. These included a novel cycle developed from analysis of the database of the World Harmonized Test Procedure (WLTP-Brake) and a short version of the Los Angeles City Traffic cycle (3h-LACT) developed in the framework of the European LowBraSys project. Disc temperature measurements using an array of embedded thermocouples revealed a large temporal and spatial non-uniformity with the radial temperature distribution depending also on the test procedure. Averaging over the duration of the cycle, it effectively reduced the influence of thermocouple positioning, allowing for more reliable quantification of the effectiveness of convective cooling. Particulate Matter (PM) emissions were similar for both cycles with PM2.5 averaging at 2.2 (±0.2) mg/km over the WLTP-Brake and 2.2 (±0.2) mg/km over the 3h-LACT, respectively. The corresponding PM10 emissions were 5.6 (±0.2) mg/km and 8.6 (±0.7) mg/km, respectively. The measurements revealed the formation of nanosized particles peaking at 10 nm, which were thermally stable at 350 °C under both cycles. Volatile nanoparticles were observed over the more demanding 3h-LACT cycle, with their emission rates decreasing with increasing the tunnel flow, suggesting nucleation of organic vapors released during braking as a potential formation process.