Dry ultra-porous cellulose fibres were obtained using a liquid exchange procedure in which water was replaced in the following order: water, methanol, acetone, and finally pentane; thereafter, the fibres were dried with Ar(g). The dry samples (of TEMPO-oxidized dissolving pulp) had a specific surface area of 130 m2 g-1 as measured using BET nitrogen gas adsorption. The open structure in the dry state was also revealed using field emission scanning electron microscopy. This dry open structure was used as a scaffold for in situ polymerization. Both poly(methyl methacrylate) and poly(butylacrylate) were successfully used as matrix polymers for the composite material (fibre/polymer), comprising approximately 20 wt% fibres. Atomic force microscopy phase imaging indicated a nanoscale mixing of the matrix polymer and the cellulose fibril aggregates and this was also supported by mechanical testing of the prepared composite where the open fibre structure produced superior composites. The fibre/polymer composite had a significantly reduced water absorption capacity also indicating an efficient filling of the fibre structure with the matrix polymer.