Particularly small graphene oxide (GO) nano sheets were synthesized and intercalated into a hydrocalumite type layered double hydroxide (Ca2Al-LDH) host structure. Synthesis of the GO intercalation compound was performed via controlled rehydration of tricalcium aluminate (Ca3Al2O6) in the presence of GO. Formation of Ca2Al-GO-LDH was evidenced from elemental, thermogravimetric, IR spectroscopy, XRD, and SAXS analysis. From the latter, an interlayer distance of 1.05 nm (d value) was found, indicating that one GO sheet is sandwiched by [Ca2Al(OH)6]+ main sheets. SAXS analysis revealed a length of the lamellar structure of 109 nm and presence of agglomerates of randomly stacked nanosized LDH fragments. The carbon content of the Ca2Al-GO-LDH particles (thickness ca. 30 nm) was significantly higher than that found for Ca2Al-OH-LDH holding surface adsorbed GO only (14 wt % vs. < 2 wt %). GO can be released easily from the inorganic host structure by anion exchange, e.g. with sulfate. The novel compound could present an interesting precursor for electronic applications after chemical reduction of GO to graphene.