Background: We have determined previously that the water extract of sugar maple bark contained an important quantity of a complex sugar. In this study, we investigated the organosolv pulping of pre-extracted bark to follow the acid conversion of sugars into major products, furfural and 5-hydroxymethyl-2-furfural (HMF), while comparing the structures of organosolv lignins. Methods: The bark particles were pre-extracted with an ethanol–water mixture or water only. The extractives-free barks were then converted into cellulosic pulp and lignin by a patented organosolv process. The composition of residual liquor was determined by using HPLC-UV. Results: The pre-extraction with water was more efficient for complex sugars recovery than with the ethanol–water system. HMF was determined to be more abundant in residual liquor than furfural after ethanol–water pre-extraction while their quantities were comparable in the residual liquor after water pre-extraction. The higher yield of HMF from ethanol–water pre-extracted bark (1.18%) than from water pre-extracted (0.69%) could be related to the efficiency of complex sugar removal during the pre-extraction step. Conclusions: The pre-extraction before pulping affected, at least in part, the composition of residual liquor in terms of HMF production. These results demonstrate how the bark can be converted into valuable products and intermediates for organic synthesis.