Ca2Fe2-xCoxO5 (0 <= x <= 1) with higher Co content, which crystallizes in a brownmillerite-type structure, is currently one of the best oxygen-evolution-reaction (OER) catalysts. Identifying the Fe/Co occupancies at the octahedral (O-h) and tetrahedral (T-d) sites in the structure is the foundation for the understanding of the role of cobalt in each site and the exploration of further improvement in the OER activity. Here, we investigate the Fe/Co distribution in Ca2FeCoO5 by means of atomic-resolution energy dispersive X-ray spectroscopy in scanning transmission electron microscopy and dynamical image simulations combined with systematic density functional theory calculations. Our careful microscopic study reveals the absence of long-range Fe/Co order within the transition-metal (TM) layers, but cobalt is slightly enriched at the T-d and O-h sites in the as-synthesized (1100 degrees C) and 800 degrees C annealed for a month samples, respectively. The observed Co site preferences are interpretable from the viewpoints of TM ionic size effect and ligand field effect, which are competitive around a crossover point at a certain temperature between 800 and 1100 degrees C. We also elucidate that the as-synthesized sample with Co enrichment at the T-d site shows the better OER activity, and the optimum annealing temperature for more OER active Ca2FeCoO5 should be higher than the crossover temperature.