This paper reports a structure analysis of the åkermanite-gehlenite solid solution. This solution is non-ideal with a negative excess volume in the entire compositional range. X-ray diffraction shows anomalous behavior of the cell parameters close to the gehlenite end-member (åk08ge92, åk35ge65). This behavior is correlated with an excess of Si and deficiency of Al with respect to the Mg content, which implies a defective, non-stoichiometric structure with Ca vacancies. Electron microscopy images have confirmed an increase in the defectivity on the atomic scale for Al-rich compositions, and single-crystal structure refinements show a correlated decrease of the tetrahedral volume preferentially occupied by Si. The incommensurate modulation, characteristic of åkermanite, has been observed also in åk95ge05, and it is still visible as diffuse scattering in åk75ge25. (210) twinning has been observed in the entire compositional range.