Tension wood is a type of reaction wood formed in response to bending or leaning of growing stems. It contains a higher glucan content and a lower amount of lignin, and is more easily broken down into fermentable sugars compared to native wood. Here, we have employed structural techniques; small-angle neutron scattering (SANS) and wide-angle X-ray diffraction (WAXD) to elucidate structural and morphological aspects of tension wood that result in higher sugar yields. SANS data exhibited a tri-modal size distribution of scattering features. The smallest size, 22 Å observed in all samples concurred with the WAXD results of the control and opposite side samples and was interpreted as the cellulose elementary microfibril diameter. The intermediate size feature of 45 Å, which is most pronounced in the tension side sample and consistent with WAXD results for tension side sample, indicates an association of neighboring elementary microfibrils to form larger crystallite bundles. The largest size, 61 Å, was not observed by WAXD and was interpreted as the presence of pores in the tension wood sample. In conclusion, clear differences were observed in the structure and morphology of tension wood compared to native wood. Cellulose crystallinity is increased, and there is evidence of pores that are not observed in native wood. It is likely that the presence of pores combined with lower lignin content in tension wood substantially improves enzyme accessibility leading to higher yields in enzymatic cellulose digestion.