Subtle crystalline structure changes of poly(butylene terephthalate) (PBT) specimens treated with an alkali solution at room temperature were investigated with the grazing incidence X‐ray diffraction (GIXRD) analysis method. A new phenomenon was found: the aqueous alkali solution induced the crystallization of the PBT polymer. Under the GIXRD analysis condition of an incidence angle of 1°, the penetration depth of the X‐ray in PBT was less than 80 μm, and this agreed well with the rough theoretical estimation. The alkali solution adopted in this study was an aqueous sodium hydroxide solution, which had a concentration of 2.5 N. Dissolved quantities of the surface layers during the alkaline treatment were found to be small. No appreciable intrinsic viscosity change due to the alkaline treatment was detected. Possible factors that might contribute to the crystallization, such as water absorption and a chemical reagent effect, were examined, and a plausible explanation for the phenomenon was developed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1938–1948, 2004