In this work, time-series analyses of the chemical composition and source contributions of PM2.5 from an urban background station in Barcelona (BCN) and a rural background station in Montseny (MSY) in northeastern Spain from 2009 to 2018 were investigated and compared. A multisite positive matrix factorization analysis was used to compare the source contributions between the two stations, while the trends for both the chemical species and source contributions were studied using the Theil-Sen trend estimator. Between 2009 and 2018, both stations showed a statistically significant decrease in PM2.5 concentrations, which was driven by the downward trends of levels of chemical species and anthropogenic source contributions, mainly from heavy oil combustion, mixed combustion, industry, and secondary sulfate. These source contributions showed a continuous decrease over the study period, signifying the continuing success of mitigation strategies, although the trends of heavy oil combustion and secondary sulfate have flattened since 2016. Secondary nitrate also followed a significant decreasing trend in BCN, while secondary organic aerosols (SOA) very slightly decreased in MSY. The observed decreasing trends, in combination with the absence of a trend for the organic aerosols (OA) at both stations, resulted in an increase in the relative proportion of OA in PM2.5 by 12% in BCN and 9% in MSY, mostly from SOA, which increased by 7% in BCN and 4% in MSY. Thus, at the end of the study period, OA accounted for 40% and 50% of the annual mean PM2.5 at BCN and MSY, respectively. This might have relevant implications for air quality policies aiming at abating PM2.5 in the study region and for possible changes in toxicity of PM2.5 due to marked changes in composition and source apportionment.