The present study investigated the characteristics of carbonaceous species in an urban background site. Real-time measurements of inorganic (sulfate, nitrate, ammonium, chloride, and black carbon [BC]) and organic submicron aerosols (OA) were carried out at the urban background site of Vilnius, Lithuania, during January–February 2014. An aerosol chemical speciation monitor (ACSM, Aerodyne Research Inc., Billerica, MA, USA) and co-located 7-λ aethalometer (AE-31, Magee Scientific, Berkeley, CA, USA) were used to analyze the chemical compositions, sources, and extinction characteristics of the PM₁. Extremely contrasting meteorological conditions were observed during the studied period due to the transition from moderately cold (~2 °C) conditions to extremely cold conditions with a lowest temperature of −25 °C; therefore, three investigation episodes were considered. The identified periods corresponded to the transition time from the moderately cold to the extremely cold winter period, which was traced by the change in the average temperature for the study days of 1–13 January, with T = −5 °C and RH = 92%, in contrast to the period of 14–31 January, with T = −14 °C and RH = 74%, and the very short third period of 1–3 February, with T = −8 °C and RH = 35%. On average, organics accounted for the major part (53%) of the non-refractory submicron aerosols (NR-PM₁), followed by nitrate (18%) and sulfate (9%). The source apportionment results showed the five most common OA components, such as traffic and heating, to be related to hydrocarbon-like organic aerosols (HOA_traffic and HOA_heating, respectively), biomass-burning organic aerosols (BBOA), local organic aerosol (LOA), and secondary organic aerosol (SOA). Traffic emissions contributed 53% and biomass burning 47% to the BC concentration level. The highest BC and OA concentrations were, on average, associated with air masses originating from the southwest and east–southeast. Furthermore, the results of the PSCF and CWT methods indicated the main source regions that contributed the most to the BC concentration in Vilnius to be the following: central–southwestern and northeastern Poland, northwestern–southwestern and eastern Belarus, northwestern Ukraine, and western Russia. However, the potential sources of OA were widely distributed.