Accordingly, this paper aims to fill that crucial gap in understanding the multiferroic behavior of B6TFMO. We describe the use of high-resolution scanning transmission electron microscopy (STEM) in conjunction with electron energy loss spectroscopy (EELS) to spatially probe atomicresolution electronic structure at the crystallographic perovskite B-site sites within the B6TFMO structure. In conjunction with first principles density functional theory (DFT) calculations of atom resolved partial density of states (PDOS), we correlate trends in crystal field splitting with changes in the extent of polar tetragonal distortion. Insights from integrated differential phase contrast (iDPC) imaging underscore the indispensable role of octahedral tilting as a facilitator for longrange magnetic order within the multiferroic B6TFMO. We use spatially resolved EELS (Figure ) to investigate the local electronic structure of the perovskite sites within its layers. measurements of the preferred locations for Ti, Mn and Fe are in agreement with previous HAADF-STEM EDX (energy dispersive X-ray analysis) chemical characterization of B6TFMO (see SI section 2). There is a significant preference for partitioning of magnetic Mn towards the center perovskite layers, while there is a distinct preference for Ti to partition to the outer perovskite layers. As demonstrated in SI Figure , the splitting between the t2g and eg peaks of the B-site transition metals is best defined within the Ti L2,3 -edge. Accordingly, the Ti L2,3 -edge was selected for further investigation of the electronic structure and subtle chemical bonding changes through the B6TFMO structure, that is from the interface of the [Bi2O2] 2+ -perovskite interface to the central of the perovskite block.