This paper provides experimental evidence for the chemical structures of aliphatically substituted and bridged polycyclic aromatic hydrocarbon (PAH) species in gas-physe combustion environments. The identification of these single- and multicore aromatic species, which have been hypothesized to be important in PAH growth and soot nucleation, was made possible through a combination of sampling gaseous constituents from an atmospheric pressure inverse coflow diffusion flame of ethylene and high-resolution tandem mass spectrometry (MS-MS). In these experiments, the flame-sampled components were ionized using a continuous VUV lamp at 10.0 eV and the ions were subsequently fragmented through collisions with Ar atoms in a collision-induced dissociation (CID) process. The resulting fragment ions, which were separated using a reflectron time-of-flight mass spectrometer, were used to extract structural information about the sampled aromatic compounds. The high-resolution mass spectra revealed the presence of alkylated single-core aromatic compounds and the fragment ions that were observed correspond to the loss of saturated and unsaturated units containing up to a total of 6 carbon atoms. Furthermore, the aromatic structures that form the foundational building blocks of the larger PAHs were identified to be smaller single-ring and pericondensed aromatic species with repetitive structural features. For demonstrative purposes, details are provided for the CID of molecular ions at masses 202 and 434. Insights into the role of the aliphatically substituted and bridged aromatics in the reaction network of PAH growth chemistry were obtained from spatially resolved measurements of the flame. The experimental results are consistent with a growth mechanism in which alkylated aromatics are oxidized to form pericondensed ring structures or react and recombine with other aromatics to form larger, potentially three-dimensional, aliphatically bridged multicore aromatic hydrocarbons.