Wood has the ability to absorb and desorb moisture, which can affect its dimensional size when in use. Limiting this can provide products with greater shape stability and less stresses on external coatings. One method that has been investigated for achieving this has been through chemical modification. In this work, the dimensional stabilisation imparted to Scots pine sapwood by chemical modification with maleic anhydride (MA) combined with sodium hypophosphite (SHP) was investigated. The influence of concentration of MA, treatment temperature and treatment period on weight percent gain (WPG) and bulking coefficient (BC) during treatment with MA and SHP of wood was studied. Furthermore, dimensional stability was determined by the water soak/oven dry method (wet-dry cycle) through five cycles in order to determine the hydrolytic stability of the ester bond and any potential cross-linking reactions. Wood blocks (20 × 20 × 10 mm) modified with MA combined with SHP exhibited lower weight loss following water soaking than unmodified blocks or MA-treated blocks. Wood blocks modified with MA and SHP showed the best anti-swelling efficiency and minimum wet-volume (water-saturated). However, as the concentration of SHP increased, dimensional stability was diminished without any increase in weight percentage gain after water soaking. When combined with FTIR results, it appeared that the modification with MA and SHP seemed to form cross-linking between wood constituents, though high concentration of SHP did not seem to result in additional cross-linking.