Polycrystalline material of a novel phase in the system CaO-Al2O3-Cr2O3 has been obtained by solid-state reactions. Chemical analysis indicated the composition CaAl2Cr2O7. Single-crystal growth of the new compound using borax as a mineralizer was successful. Diffraction experiments at ambient conditions on a crystal with composition CaAl2.13Cr1.87O7 yielded the following basic crystallographic data: space group P 3, a = 7.7690(5) angstrom, c = 7.6463(5) angstrom, V = 399.68(6) angstrom(3), Z = 3. Structure determination and subsequent least-squares refinements resulted in a residual of R(|F|) = 2.3% for 1440 independent observed reflections and 113 parameters. To the best of our knowledge, the structure of CaAl(2.13)Cr(1.87)O(7 )or CaAl2Cr2O7 represents a new structure type. It belongs to the group of double layer structures where individual double layers contain octahedrally and tetrahedrally coordinated cation positions. Linkage between neighboring sheet packages is provided by additional calcium cations. Furthermore, thermal expansion has been studied in the interval between 29 and 790 degrees C using in situ high-temperature single-crystal diffraction. No indications for a structural phase transition were observed. From the evolution of the lattice parameters the thermal expansion tensor has been obtained. A pronounced anisotropy is evident. The response of structural building units to variable temperature has been discussed.