α-Pinene (C10H16) represents one of the most important biogenic emissions in the atmosphere. Its oxidation products can significantly contribute to the secondary organic aerosol (SOA) formation. Here, we report on the formation mechanism of C19 and C20 accretion products from α-pinene oxidation, which are believed to be efficient SOA precursors. Measurements have been performed in a free-jet flow system. Detection of RO2 radicals and accretion products was carried out by recent mass spectrometric techniques using different ionization schemes. Observed C10-RO2 radicals from α-pinene ozonolysis were O,O-C10H15(O2) xO2 with x = 0, 1, 2, 3 and from the OH radical reaction HO-C10H16(O2)αO2 with α = 0, 1, 2. All detected C20 accretion products can be explained via the accretion reaction RO2 + R'O2 → ROOR' + O2 starting from the measured C10-RO2 radicals. We speculate that C19 accretion products are formed in an analogous way assuming CH2O elimination. Addition of isoprene (C5H8), producing C5-RO2 radicals, leads to C15 accretion products formed via cross-reactions with C10-RO2 radicals. This process is competing with the formation of C19/C20 products from the pure α-pinene oxidation. A similar behavior has been observed for ethylene additives that form C12 accretion products. In the atmosphere, a complex accretion product spectrum from self- and cross-reactions of available RO2 radicals can be expected. Modeling atmospheric conditions revealed that C19/C20 product formation is only reduced by a factor of 1.2 or 3.6 in isoprene-dominated environments assuming a 2- or 15-fold isoprene concentration over α-pinene, respectively, as present in different forested areas.