α-Form hydrated crystals form a lamellar gel in which the alkyl chains of the amphiphilic molecules are hexagonally arranged within bilayers below the gel–liquid crystal phase transition temperature. In practice, the lamellar gel network with excess water is called an “α-gel”, particularly in the cosmetics industry. In this study, the hydration or water sorption of amphiphilic materials in water vapor was assessed using a humidity-controlled quartz crystal microbalance with dissipation monitoring (QCM-D) technique. The amphiphilic materials used in this study were hexadecyl phosphate salts neutralized with L-arginine (C16P-Arg), CsOH (C16P-Cs), KOH (C16P-K), and NaOH (C16P-Na). Small- and wide-angle X-ray scattering measurements revealed that C16P-Arg and C16P-Cs yielded α-form hydrated crystals. Humidity-controlled QCM-D measurements demonstrated that C16P-Arg and C16P-Cs more readily underwent hydration or water sorption than C16P-K and C16P-Na. The key conclusion is that the significant hydration ability of C16P-Arg and C16P-Cs promotes the formation of the corresponding α-form hydrated crystals.