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Observation-based data of primary and secondary organic carbon in ambient particulate matter (PM) are essential for model evaluation, climate and air quality research, health effect assessments, and mitigation policy development. Since there are no direct measurement tools available to quantify primary organic (POC) and secondary organic carbon (SOC) as separate quantities, their estimation relies on inference approaches using relevant measurable PM constituents. In this study, we measured hourly carbonaceous components and major ions in PM 2.5 for a year and a half in suburban Hong Kong from July 2020 to December 2021. We differentiated POC and SOC using a novel Bayesian inference approach. The hourly POC and SOC data allowed us to examine temporal characteristics varying from diurnal and weekly patterns to seasonal variations, as well as their evolution characteristics during individual PM 2.5 episodes. A total of 65 city-wide PM 2.5 episodes were identified throughout the entire study period, with SOC contributions during individual episodes varying from 10 % to 66 %. In summertime typhoon episodes, elevated SOC levels were observed during daytime hours, and high temperature and NOx levels were identified as significant factors contributing to episodic SOC formation. Winter haze episodes exhibited high SOC levels, likely due to persistent influences from regional transport originating from the northern region to the sampling site. Enhanced SOC formation was observed with increase in the nocturnal NO3 radical (indicated by the surrogate quantity of [ NO2 ][ O3 ]) and under conditions characterized by high water content and strong acidity. These results suggest that both NO3 chemistry and acid-catalyzed aqueous-phase reactions likely make notable contributions to SOC formation during winter haze episodes. The methodology employed in this study for estimating POC and SOC provides practical guidance for other locations with similar monitoring capabilities in place. The availability of hourly POC and SOC data is invaluable for evaluating and improving atmospheric models, as well as understanding the evolution processes of PM pollution episodes. This, in turn, leads to more accurate model predictions and a better understanding of the contributing sources and processes. [ABSTRACT FROM AUTHOR]