This study was to refined the crystal structure of solid solution to determine the position and amount of Al in diopside and to relate crystal structure changes and properties of solid solution. Single crystals of the solid solution in the system CaO.MgO.$2 SiO_2-Al_2O_3$ were made from the melt with slow cooling and used to refine the structure. The following were obtained. 1. Tetrahedra rotated around axis parallel to the direction which the angle 03-03-03 became small. 2. Tetrahedron became large and regular. Average T-O bond distance increased 0.53 percent. 3. M1 octahedron became small and average M1-O bond distance decreased 1.1 percent. 4, M2 polyhedron became small and average M2-O bond distance decreased 0.37 percent Polythedron was affected not so much compared with any cation site. 5. Distance between metal ions distances between T and oxygens which were coordinated with M2 and meighboring tetrahedron distances between M2 and oxygens which coordinated with M1 and M2 were not changed almost. 6. $Al^{3+}$ substituted 4Mg^{2+}$ and <TEX>$Si^{4+}$</TEX. with same amount.