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Gigantic magnetoelectric coupling between ferroelectricity and magnetism has been demonstrated in a number of rare-earth perovskite oxides such as manganites, cobaltates, nickelates and ironates with either hexagonal or orthorhombic structures. In terms of applications, multiferroics have shown their distinction as, (i) special layer in a spintronic device to enable electric field control of magnetization and (ii) novel solid-state refrigerant due to their novel multicaloric cooling property. In this work, we have carried out a comprehensive study on selected rare-earth based double perovskites with Co and Mn occupied at the B-site to investigate the multiferroicity, phase separation and magnetic field induced phenomena like magnetodielectric, multicaloric, and exchange bias effects in double perovskite systems. Determining the intrinsic and extrinsic contributions to magnetodielectric effect to elucidate the authenticity on intrinsic ferroelectricity and magnetoelectric coupling is one of the central theme of this book.