Quite recently, the Ioncell-F process, a novel and promising Lyocell fibre process, has been developed. The ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH]OAc) utilized in this process, was identified as an excellent cellulose solvent for dry-jet wet fibre spinning. Fibres spun from cellulose-[DBNH]OAc solution have shown excellent mechanical properties. Herein, various structural features of these ionic liquid-based fibres were analyzed and correlated with their mechanical properties. The highest slope of tenacity increase of these Ioncell-F fibres (from birch wood) observed at low draw ratios (DRs), while a continuous but slower increase occurs to partly very high draws. The improvements in the mechanical properties do not seem to correlate with changes in the crystallite size or the crystalline orientation based on wide-angle X-ray scattering (WAXS) results. More significant differences were seen for the sample crystallinity, the amorphous orientation (measured by birefringence), the orientation of the voids, the specific surface (measured by small-angle X-ray scattering (SAXS)), and the sorption/desorption properties of the fibres.