We have investigated the reactivities of various metal fluorides in the nucleophilic fluorination of 2-(3-methanesulfonyloxypropyl)naphthalene (1) as a model compound in the presence of 1-n-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)]). The higher periodic alkali metal fluorides demonstrate greater reactivity. The fluorination using CsF among the alkali metal fluorides was completed in 20 min, affording the desired product 2-(3-fluoropropyl)naphthalene (2a, 95%) without any byproducts. However, the fluorinations using alkali earth, transition, and low periodic alkali metal fluorides under the same conditions occurred rarely or not at all. We have also carried out the various facile nucleophilic substitutions such as halogenations, acetoxylation, nitrilation, and alkoxylations of mesyloxyalkane 1 and 2-(3-bromopropyl)naphthalene (6) at the primary aliphatic position using the potassium halides, acetate, cyanide, and alkoxides, respectively, in the presence of ionic liquids. These reactions provided the desired products, such as 2-(3-halopropyl)naphthalenes 5-7 (95% for Cl, 96% for Br, and 93% for I), 2-(3-acetoxypropyl)naphthalene (8, 95%), 2-(3-cyanopropyl)naphthalene (9, 93%), and 2-(3-methoxypropyl)naphthalene (10, 92%).