Polycrystalline Ca2Fe2-xAlxO5 (x = 0-1.4) samples were prepared by conventional solid-state reactions. Their crystalline/electronic structures and magnetic properties were characterized in detail. Powder X-ray diffraction analyses revealed that the samples crystallized in orthorhombic brownmillerite-type structures with the occurrence of the Pcmn-Ibm2 phase separation in the region between x = 0.4 and 0.6. The results obtained from analyzing Raman scattering and X-ray-absorption fine-structure spectra also indicated this phase separation. Although x in Ca2Fe2-xAlxO5 varies in a wide range from 0 to 1.4, the +3 oxidation state of Fe remained almost unchanged. Magnetization measurements revealed that all Ca2Fe2-xAlxO5 samples have weak ferromagnetic order, and both the saturation magnetization and coercive force are dependent on the temperature, x, and structure phases.