We report on the synthesis and exfoliation of mn(II)Al(III) sulfonate and sulfate layered double hydroxides (LDHs) and their combination with graphene oxide by charge-directed self-assembly. The synthesis of the LDH compounds has been accomplished either directly by coprecipitation of the respective hydroxides with sulfonate anions or by ion-exchange of the chloride-containing LDH with sodium dodecylsulfate. Exfoliation of the bulk material in formamide yields colloidal suspensions of positively charged nanosheets with lateral dimensions of tens to hundreds of nanometers and thicknesses down to 1.3 nm, ascertained by TEM and AFM. Flocculation of the LDH nanosheets with an aqueous graphene oxide suspension yields a hybrid material that can be converted to a reduced graphene oxide/LDH composite by hydrazine reduction. The hybrid materials were tested for pseudocapacitive electrochemical storage capacity and electrocatalytic oxygen evolution reactions and showed significant increases compared to the pristine materials.