Source apportionment of atmospheric PM1 is important for air quality control, especially in urban areas where high mass concentrations are often observed. Chemical analysis of molecular inorganic and organic tracer compounds and subsequently data analysis with receptor models give insight on the origin of the PM1 sources. In the present study, four source apportionment approaches were compared with an extended database containing inorganic and organic compounds that were measured during an intensive sampling campaign at urban traffic and urban background sites in Barcelona. Source apportionment of the combined database, containing both inorganic and organic compounds, was compared with more conventional approaches using inorganic and organic databases separately. Traffic emission sources were identified in all models for the two sites. The combined inorganic and organic databases provided higher discrimination capacity of emission sources. It identified aerosols generated by regional recirculation of biomass burning, secondary biogenic organic aerosols, harbor emissions, and specific industrial emissions. In this respect, this approach identified a relevant industrial source situated at NE Barcelona in which a waste incinerator plant, a combined-cycle power plant, and an industrial glass complex are located. Models using both inorganic and organic molecular tracer compounds improve the source apportionment of urban PM.