Polycyclic aromatic hydrocarbon growth from cyclopentadiene (CPD) pyrolysis was investigated using a laminar flow reactor operating in a temperature range of 600 to 950°C. Major products from CPD pyrolysis are benzene, indene and naphthalene. Formation of observed products from CPD is explained as follows. Addition of the cyclopentadienyl radical to a CPD π-bond produces a resonance-stabilized radical, which further reacts by one of three unimolecular channels: intramolecular addition, C-H bond β-scission, or C-C bond β-scission. The intramolecular addition pathway produces a 7-norbornenyl radical, which then decomposes to indene. Decomposition by C-H bond β-scission produces a biaryl intermediate, which then undergoes a ring fusion sequence that has been proposed for dihydrofulvalene-to-naphthalene conversion. In this study, we propose C-C bond β-scission pathway as an alternative reaction channel to naphthalene from CPD. As preliminary computational analysis, Parametric Method 3 (PM3) molecular calculation suggests that intramolecular addition to form indene is favored at low temperatures and C-C bond β-scission leading to naphthalene is predominant at high temperatures.