Perovskites and perovskite-related oxides are one of the most fertile family of materials among transition metal oxides, for a materials designer to pick up for the integration of innovative functions. The broad range of properties associated with the perovskite crystal structure can be manipulated to control many technologically promising phenomena related to superconductivity, exchange bias, multiferroicity, and photovoltaics etc. In the present work, several features such as compositional tuning, octahedral tilting/rotations and point defects were controlled and a detailed correlation between structural and corresponding physical properties (especially on magnetic properties) are established and illustrated using three different perovskite structured oxide systems. The key findings include (i) composition controlled quasi 2D layered perovskites with multiple magnetic ions at B-site (SrLaFe0.25Mn0.25Co0.5O4 and SrLaFe0.5Mn0.25Co0.25O4) towards tuning of Giant Exchange Bias; (ii) temperature dependent structural studies and phase transition in CaPrFe0.5Co0.5O4 and HoCrO3 and (iii) observation of magneto-dielectric coupling and pyroelectric current anomaly in point defect controlled HoCrO3. Hence the thesis focuses on the manipulation of composition control as well as local octahedral distortions and explores the fundamental structure-property relationships which can be considered for creating novel functional perovskite oxides.​