The intramolecular Curtius rearrangement suffers from a high reaction temperature, low yields, tedious product isolation, and difficult scale up. This study presents a room-temperature Curtius rearrangement that can be novelly driven by the HFIP solvent, followed by light-illuminated intramolecular cyclization. Such a mild reaction allows for the preparation of various fused pyridone derivatives with diverse substituent groups that have rarely been incorporated by previous methods. The roles of HFIP and light are investigated by a set of control experiments through a combination of IR and NMR titration. Furthermore, using the substituted fused pyridones as unnatural bases, we can obtain a panel of new nucleotides.