The Dy 1− x Ca x CoO 3− y (0.00⩽ x ⩽1.00) compounds have been prepared by a drip pyrolysis technique. The electronic structure and the geometric environment of the solid solutions are determined with Co K-edge X-ray absorption near edge structure (XANES). In the absorption edge region, it has been observed that three peak groups correspond to the 1s → 4p main transition allowed by the electric dipole matrix, the shakedown transition of ligand to metal charge transfer process, and 1s → 3d quadrupole allowed transition, respectively. In our comprehensive crystallographic investigation of the system, it is found that the DyCoO 3 compound has a typical GdFeO 3 structure with the space group of Pbnm. The compounds of x = 0.75 and 1.00 are formed with more than twice the size of an ideal perovskite unit cell and those of x = 0.25 and 0.50 include a microscopic binary phase of CaCoO 2.50. The electrical conductivities depend on the Ca 2+ ion content which affects the distortion of oxygen octahedra along the c-axis and then the transition of π ∗ to σ ∗ energy level. As a result of magnetic measurement, it is found out that low spin states of Co 3+ ions are converted to high spin totally or partially around 550 K in the compounds of x = 0.00−0.50. The constant ratios of low-high spin states at x = 0.75 and 1.00 are preserved in the given temperature region.