Polycyclic aromatic azomethine ylide (PAMY) is a versatile building block for the bottom-up construction of unprecedented nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs). Here, we demonstrate the 1,3-dipolar cycloaddition between PAMY and 1,4-diphenylbut-2-yne-1,4-dione as well as the subsequent condensation reaction with hydrazine, which led to synthesis of unique N-PAHs with a phenyl-substituted pyrrolopyridazine core (PP-1 and PP-2). The molecular structures of pristine PP-1 and tert-butyl-substituted PP-2 were verified by NMR and mass spectroscopy. Moreover, the structure of PP-2 was unambiguously elucidated by X-ray single crystal analysis. The optoelectronic properties were investigated by solvent-dependent UV-Vis absorption and fluorescence emission spectroscopy as well as cyclic voltammetry. Additionally, the density functional theory (DFT) calculations exhibited a push-pull behavior for PP-1 and PP-2. Furthermore, the in situ EPR/UV-Vis-NIR spectroelectrochemistry allowed the detailed insight into the spectroscopic properties and spin distribution of radical cation species of PP-2.