LAUSR

Control of BO6 octahedral rotations at the heterointerfaces of dissimilar ABO3 perovskites has emerged as a powerful route for engineering novel physical properties. However, its impact length scale is constrained at 2–6 unit cells close to the interface and the octahedral rotations relax quickly into bulk tilt angles away from interface. Here, a long‐range (up to 12 unit cells) suppression of MnO6 octahedral rotations in La0.9Ba0.1MnO3 through the formation of superlattices with SrTiO3 can be achieved. The suppressed MnO6 octahedral rotations strongly modify the magnetic and electronic properties of La0.9Ba0.1MnO3 and hence create a new ferromagnetic insulating state with enhanced Curie temperature of 235 K. The emergent properties in La0.9Ba0.1MnO3 arise from a preferential occupation of the out‐of‐plane Mn d 3z 2−r 2 orbital and a reduced Mn eg bandwidth, induced by the suppressed octahedral rotations. The realization of long‐range tuning of BO6 octahedra via superlattices can be applicable to other strongly correlated perovskites for exploring new emergent quantum phenomena.