Spent coffee grounds (SCG), the residual materials obtained during the processing of raw coffee powder to prepare instant coffee, are the main coffee industry residues. In the present work, this material was chemically characterized and subsequently submitted to a dilute acid hydrolysis aiming to recover the hemicellulose sugars. Reactions were performed according to experimental designs to verify the effects of the variables H2SO4 concentration, liquid-to-solid ratio, temperature, and reaction time, on the efficiency of hydrolysis. SCG was found to be rich in sugars (45.3%, w/w), among of which hemicellulose (constituted by mannose, galactose, and arabinose) and cellulose (glucose homopolymer) correspond to 36.7% (w/w) and 8.6% (w/w), respectively. Optimal conditions for hemicellulose sugars extraction consisted in using 100 mg acid/g dry matter, 10 g liquid/g solid, at 163 °C for 45 min. Under these conditions, hydrolysis efficiencies of 100%, 77.4%, and 89.5% may be achieved for galactan, mannan, and arabinan, respectively, corresponding to a hemicellulose hydrolysis efficiency of 87.4%.