The temperature dependent structural studies carried out on the spin-correlated system A2FeCoO6 (A= Sm, Eu, Dy and Ho) or AFCO (A= Sm, E, D and H), using synchrotron radiation is presented. Owing to the large absorption cross-sections of the rare earths; Eu, Sm and Dy for neutrons, synchrotron radiation is one of the best available candidates for probing the system. The perovskite phase formation is inferred from laboratory XRD with Cu Kα source. The temperature dependent synchrotron X-ray diffraction (SXRD) experiments show the coexistence of monoclinic P21/n and orthorhombic Pbnm phases in Ho and Dy, while Eu and Sm are formed in single phase Pbnm. The temperature dependent DC magnetization measurements infer the presence of many interesting features such as thermal hysteresis, magnetic irreversibility, spin re-orientation, re-entrant magnetization and negative magnetization. © 2017 Author(s).