Cellulose is a basic cell wall constituent and an abundant natural product of economic significance. Bolls picked at different times of the day and at various stages of development were quickly frozen in the field, stored frozen, and freeze dried. Later the fibers are re-hydrated, and extracted with cold water, to recover the soluble sugars including sucrose, the sucrosyl oligosaccharides and other hypothesized precursors of cell wall biosynthesis. A second extraction with hot, dilute HCl removed a series of oligomers, which consist primarily of glucose, but also may contain small amounts of mannose, galactose and arabinose. The relative abundance of the oligomers vary with time of day, suggesting a diurnal rhythm of cell wall biosynthesis. The extracted oligomers are most abundant at the onset of secondary cell wall biosynthesis, and then decline with boll maturation. In this research, we subjected the oligomers to additional fractionation by alcohol precipitation to yield populations eluting across a time gradient in high pH anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD). The oligomeric precipitates were subsequently resuspended and degraded by a specific endo ß-1,4-glucanase to yield glucose and the first oligomer eluted in the series. The abundance of these glycans corresponds with developmental age. In the early stages of secondary cell wall biosynthesis the relative abundance of the shorter chain length glycans is relatively high, then decreases from 21 to 25 (21>22>25) days post anthesis (DPA). During the same period the relative abundance of the longer chain length glycans increases, with a maximum at 22 DPA, then decreases (21<22>25 DPA). This pattern suggests that there are populations of oligomers differing in chain length. The populations appear to shift progressively to those of longer chain length as development proceeds. These data are consistent with a model wherein the oligomers are synthesized and incorporated into the secondary cell wall by means of a linkage or linkages that are not cleaved by the dilute acid extraction. Alcohol fractionation of the oligomers increases our ability to monitor cotton fiber development and to determine environmental effects on fiber yield and quality.