Although several studies, including our own (Hodgetts et al., 2015), have demonstrated that perceptual discrimination of complex scenes relies on an extended hippocampal network, distinct from the anterotemporal network supporting the perceptual discrimination of faces, we currently have limited insight into the specific functional and structural properties of these networks. Here, combining electrophysiological (magnetoencephalography, MEG) and microstructural (multi-shell diffusion MRI, dMRI) imaging in healthy human adults, we show that both hippocampal theta power modulation and fibre restriction of the fornix (a major input/output pathway of the hippocampus) independently related to accuracy during scene, but not face, perceptual discrimination. Conversely, inferior longitudinal fasciculus (a long-range occipito-anterotemporal tract) tissue properties correlated with face, but not scene, oddity discrimination accuracy. Our results provide new mechanistic insight into the neurocognitive systems underpinning complex scene and face perception, providing support for multiple-system representation-based accounts of the medial temporal lobe.