With the optimal conditions in hand, the substrate scope was investigated (Scheme 1). Various 3-arylpyrazolopyridines were examined: Methyl (1B), tert-butyl (1C), and phenyl (1D) at the para-position on the aryl group gave the ring-opening fluorinated products 2B-2D in moderate yields. It should be noted that fluorination of these aryl groups was detected. When using trimethylphenyl (1E) and naphthyl (1F) starting materials, the corresponding products 2E and 2F were obtained in moderate yields, and occurred decomposition of 1E or fluorinated the aryl group of 1F (less than 10% yields). The reaction showed good functional group tolerance in the presence of formyl (1G), acetyl (1H), cyano (1I), trifluoromethyl (1J), nitro (1K), and chloro (1L) groups, as the reaction worked to give the corresponding products 2G-2L in excellent yields. Next, 3alkylpyrazolopyridines were investigated. The fluorination using bicyclic azaarenes bearing alkyl groups (1M and 1N) or acetal (1O) proceeded smoothly to give the corresponding fluorinated products 2M-2O in moderate to excellent yields. Pyrazolopyridines with alkyl acetate (1P), cyano (1Q), and ethylcarboxylate (1R) afforded the corresponding products (2P-2R) in good yields. Pyrazolopyridine carboxylates were also examined. Substrates with alkyl groups including alkene (1U) and alkyne (1W) remained intact to give products 2S-2X in high yields. Carboxylic acid 1Y also reacted well, but the product was difficult to purify, resulting in a low yield of 2Y. In the case of compounds with amides such as 1Z, deamidation occurred to give 3-fluoropyrazolopyridine as a byproduct. Therefore, the fluorinated product 2Z was obtained in moderate yield (39%) by reacting at a lower temperature (-30 °C). Furthermore, azaarenes 1AA and 1AB derived from probenecid and estrone also gave fluorinated compounds 2AA and 2AB in high yields. Of note, in the case of an unsaturated ester or iodine at the C3 position, the desired fluorinated product could not be obtained, giving a complex mixture.