Abstract: Compositions are disclosed for dewatering mixtures of petroleum and water. The compositions comprise one or more of the following: an unreacted polysaccharide component; and one or both of a polysaccharide component reacted with a hydrophilic component and a polysaccharide component reacted with a hydrophobic component. The compositions may also include viscosifying agents or stabilizers to stabilize the compositions against separation, for example, prior to use. In particularly preferred embodiments the invention is drawn to compositions for breaking an emulsion; such compositions comprising a carbohydrate component containing a cationic starch joined to a hydrophobic moiety, providing the carbohydrate component oil solubility. The composition may optionally comprise one or more additional demulsifier selected from, without limitation, salts (such as a polyaluminum chloride, an aluminum chlorohydrate, an alum, etc.