The time course and pattern deposition of the cell wall polysaccharides in the starchy endosperm of wheat (Triticum aestivum cv. Recital) during grain development was studied using Fourier transform infrared microspectroscopy (micro-FTIR). Three stages of grain development identified as key stages for cell wall construction were retained as follows: the end cellularization, the beginning of cell differentiation, and the beginning of maturation. Micro-FTIR revealed that beta-(1 -> 3),(1 -> 4) glucans and arabinoglactan proteins are the main cell wall components of enclosperm at the end of the cellularization stage, whereas arabinoxylans (AX) appeared only at the cell differentiation stage. Past the differentiation stage, FTIR spectra were dominated by AX features. Cell walls at the beginning of cell differentiation and at enclosperm maturation could be distinguished by spectral features that were ascribed to AX substitution. AX appeared more substituted at the beginning of cell differentiation. Moreover, a difference in the degree of AX substitution was found between peripheral and central parts of the grain at the cell differentiation stage; AX in central cells was less substituted. Thus, dramatic changes in enclosperm cell wall composition were detected during wheat grain development with respect to both the relative occurrence of individual constituents and the fine structure of the AX.