Polycyclic aromatic hydrocarbons (PAHs) demonstrated unusual weak C–H⋯F type H-bonding interaction with meso-substituted Bodipy dyes (1–3) in ethanol medium. Isosbestic absorptions and enhancement of emission of Bodipy were spectroscopically detected with three chosen PAHs (naphthalene, anthracene and phenanthrene). IR, ¹H and ¹⁹F NMR, cyclic voltammetry, powder X-ray and Monte Carlo simulation of adducts confirmed interaction of PAHs via C–H⋯F type H-bonding with the chosen dyes.