This thesis investigates the connectivity of oxygen octahedra in epitaxial heterostructures, showing that their rotational amplitude in thin films can be tuned over a range from a few unit cells to several nanometers by balancing epitaxial strain and octahedral connectivity. Focusing on LaVO₃/DyScO₃, we demonstrate that adjusting growth conditions alters the effective strain on LaVO₃ films. Under compressive strain, both misfit strain and connectivity favor the [110] orientation, while under tensile strain, they compete. Beyond a critical thickness, strain dominates, inducing a shift in preferred orientation to [001], necessitating a structural switching plane. In LaVO₃/(110)GdScO₃, larger tensile strain requires stricter growth control to maintain high crystallinity and avoid defect-related relaxation. Lastly, we explore SrRuO₃/DyScO₃ to tune ferromagnetism via crystal orientation. SrRuO₃ adopts a different orthorhombic symmetry, resolving the strain-connectivity conflict without switching plane; magnetization remains in-plane, with no significant change in magnetic properties detected.