Agrosilvopastoral waste, regarding agriculture and agro-industry sectors, is pointed as a promising sustainable raw material for biofuels production, specially concerning exploitation of lignocellulosic organic residues for fermentable sugars and cellulosic ethanol output, being therefore necessary to investigate the potential of these substrates concerning chemical composition, since many of them were not reported yet in literature. Being so, this paper presents a study of chemical composition and enzymatic hydrolysis of wastes from the four main crops in Maranhão, Brazil (soy, cassava, rice and corn) which are usually underutilized or abandoned in the field. The results of enzymatic hydrolysis were satisfactory for both soy and particularly corn residues, which presented total reducing sugars (TRS) percentage greater than 50% in comparison with pure cellulose.