La1/3Ca2/3FeO3 with unusually-high-valence Fe3.67+ was synthesized at a high pressure and high temperature. The compound crystallizes in a root 2ax2ax root 2a perovskite cell in which the La and Ca ions at the A site are disordered. At 217 K the Fe3.67+ shows charge disproportionation to Fe3+ and Fe5+ in a ratio of 2:1, and this disproportionation is accompanied by transitions in magnetic and transport properties. The charge-disproportionated Fe3+ and Fe5+ are arranged along the < 111 > direction of the cubic perovskite cell. The local electronic and magnetic environments of Fe in La1/3Ca2/3FeO3 are quite similar to those of Fe in La1/3Ca2/3FeO3, and the 2:1 charge disproportionation pattern of Fe3+ and Fe5+ in La1/3Ca2/3FeO3 is also the same as that in La1/3Ca2/3FeO3.