Brownmillerite-type oxides Ba₂In_2-x-yMn_xAl_yO_5+x (0 ≤ x ≤ 0.6, 0 ≤ y ≤ 0.5) were prepared at 1300°C through solid-state reaction. X-ray diffraction (XRD) analysis showed that the structure symmetry evolved from orthorhombic to cubic with increasing Mn and Al contents. When y was greater than 0.3, peaks associated with small amounts of BaAl₂O₄ and Ba₂InAlO₅ impurities were observed in the XRD patterns. When substituted with a small amount of Mn (x ≤ 0.3), the Ba₂In_2-x-yMn_xAl_yO_5+x samples exhibited an intense turquoise color. The color changed to green and dark-green with increasing Mn concentration. UV–vis absorbance spectra revealed that the color changed only slightly upon Al doping. The valence state of Mn ions in Ba₂In_2-x-yMn_xAl_yO_5+x was confirmed to be +5 on the basis of X-ray photoelectron spectroscopic analysis. According to this analysis, the intense turquoise color of the Ba₂In_2-x-yMn_xAl_yO_5+x samples is rooted in the existence of Mn⁵⁺; thus, the introduction of Al does not affect the optical properties of the compounds.