For the biphenyltetracarboxylic dianhydride (BPDA)-based polyimide thin films, the water sorption behaviors were gravimetrically investigated by using a thin film diffusion analyzer. The water sorption behaviors of the polyimide thin films are quite different and strongly dependent upon the sort of polyimide. The diffusion coefficients of the polyimide thin films vary in the range of 1.6 x 10(-10) to 12.4 x 10 (10)cm(2)/s and the water uptakes vary from 1.52 to 5.25 wt %;. Both the diffusion coefficient and water uptake of the polyimide thin films are in the increasing order: BPDA-pPDA < BPDA-p,p'ODA < BPDA-p,m'ODA < BPDA-mPDA BPDA-p,p'DDS < BPDA-m,m'DDS. Specifically, the polyimide films with para-oriented linkages in backbone structure showed relatively lower diffusion coefficient and water uptake than the corresponding polyimide films with meta-oriented linkages because of the well developed crystalline structure and good intermolecular chain ordering. In addition, the polyimide thin films having higher chain order showed relatively lower diffusion coefficient and water uptake. The crystallinity and intermolecular chain ordering in the morphological structure are critical parameters in controlling the water sorption behaviors of the polyimide thin films.