A 2D-liquid chromatographic fractionation method was combined with direct infusion electrospray ionization Fourier transform-ion cyclotron resonance mass spectrometry to better resolve the high complexity of the organic material in atmospheric particles. The number of assigned molecular formulas increased by a factor of 2.3 for the fractionated sample (18 144) compared to a bulk sample analysis without fractionation (7819), while simultaneously allowing the identification of 71 240 isomeric compounds. Accounting for these isomers has an impact on the means and distributions of different descriptive sample parameters. More than 15 000 compounds were exclusively identified in the fractionated sample providing insights regarding the formation of organosulfates, reduced N-containing compounds, and polyaromatic compounds. Further, a new method for assigning organonitrates and poly-organonitrates based on Kendrick mass defect analysis is presented. The current study implicates that analytical separation leads to much more detailed insights into particle organics composition, while more commonly applied direct infusion MS studies can strongly underestimate composition complexity and lead to biased assignments of bulk organic properties. Overall, the particle organics composition is far more complex than previously shown, while separation through better chromatographic techniques helps to understand formation processes of atmospheric particle constituents.