The moisture-induced degradations during the use of paper are of growing concern for the existing paper materials stored in libraries, archives and museums. Knowing the moisture profiles is therefore a primary step in order to understand paper deterioration and give an assessment of degradation rate of library collections in their preservation. In this paper, the theoretical models based on 2-D scanning electron microscope real image microstructure were established for describing moisture transport in paper sheet in response with external humidity and the moisture diffusion profiles. The acid-catalyzed hydrolysis kinetic in combination with moisture diffusion theory gave the complementary explanation for the time-dependent natural aging process of a paper sheet and book stacks. The differential equations were solved by a numerical approach based on the finite element method implemented in commercial COMSOL Multiphysics. The 2-D simulation results, with a mesh based directly on SEM characterization of microstructure, could show the equilibrium moisture contents and the degradation rates as a function of relative humidity in cellulose pores and cellulose fibers across the transverse section of paper. For the stacks composed of books, the air gaps between the books provided convenient channels for diffusion and transport, accelerating the moisture transport process in the book stacks.