Interest in making chiral polycyclic aromatic hydrocarbons (PAHs) or nanographenes (NGs) has greatly increased recently. To date, a majority of chiral nanocarbons have been designed based on helical chirality. Here, we describe a novel atropisomeric chiral oxa-NG 1 by the selective dimerization of naphthalene-containing, hexa-peri-hexabenzocoronene (HBC)-based PAH 6. The photophysical properties of the oxa-NG 1 and monomer 6 were investigated, including UV-vis absorption (λ_max = 358 nm for 1 and 6), fluorescence emission (λ_em = 475 nm for 1 and 6), fluorescence decay (15 vs. 16 ns), and fluorescence quantum yield, and it was found that the photophysical properties of the monomer are nearly maintained in the NG dimer due to its perpendicular conformation. Single-crystal X-ray diffraction analysis shows that both enantiomers cocrystallize in a single crystal, and the racemic mixture can be resolved by chiral high-performance liquid chromatography (HPLC). The circular dichroism (CD) spectra and circularly polarized luminescence (CPL) of the enantiomers of 1-S and 1-R were studied and the CD and CPL spectra exhibited opposite Cotton effects and fluorescence signals. Density functional theory (DFT) calculations and HPLC-based thermal isomerization results showed that the racemic barrier is as high as 35 kcal mol⁻¹, suggesting a rigid chiral nanographene structure. Meanwhile, in vitro studies indicated that oxa-NG 1 is an efficient photosensitizer for white-light-induced singlet oxygen generation.