Molecular crystals of dicoronylene (C48H20), a member of very large polycyclic aromatic hydrocarbons (PAHs), exhibits strong red fluorescence under ambient conditions. This strong fluorescence induced by visible light excitation obscures entire Raman spectrum of dicoronylene. We employed in-situ high-pressure photoluminescence spectroscopy to observe a reversible piezochromic effect, in which the fluorescence exhibits a drastic red-shift with a rapid quenching of intensity. Above 4 GPa, under red-shifted and reduced fluorescence, hidden Raman modes are observed with 532 nm green laser up to 20 GPa. In this work, we show that the application of pressure can finely tune the fluorescence of dicoronylene, allowing the observation of the Raman spectrum with an appropriate laser wavelength and we discovered that dicoronylene has high chemical stability among PAH molecules with multiple aromatic rings.