The transformation of biomasses from agro-industrial waste can significantly impact the production of green chemicals from sustainable resources. Pectin is a biopolymer present in lignocellulosic biomass as Orange Peel Waste (OPW), and has possibilities for making platform compounds such as furfural for sustainable chemistry. In this work, we studied the transformation to furfural of OPW, pectins, and D-galacturonic acid (D-GalA), which is the main component of pectin. We analyzed pectins with different degrees of esterification (DE) in a one-pot hydrolysis reaction system and studied the differences in depolymerization and dehydration of the carbohydrates. The results show that the production of furfural decreases as the DE value increases. Specifically, low DE values favor the formation of furfural since the decarboxylation reaction is favored over deesterification. Interestingly, the furfural concentration is dependent upon the polysaccharide composition of pentoses and uronic acid. The obtained concentrations of furfural, D-xylose, and L-arabinose remained the same when the galacturonic acid was fed either as a polymer or a monomer. OPW is proposed as a feedstock in a biorefinery, in which on a per kg OPW dry basis, 90 g of pectin and 15 g of furfural are produced in the most favorable case. We conclude that the co-production of pectin and furfural from OPW is economically feasible.