Two-dimensional transition metal dichalcogenides (TMDs) are an exciting class of materials that let us explore how electronic properties are at reduced dimensionality and at material interfaces. In this thesis, scanning tunnelling microscopy (STM) and spectroscopy are employed to investigate the electronic properties of thin exfoliated MoS₂ and VSe₂ on gold substrates. To enable systematic and reproducible studies, ultra-flat template-stripped gold substrates were developed, allowing the exfoliation of millimetre-sized monolayer flakes, including materials that are otherwise difficult to isolate, such as VSe₂. The polycrystalline nature of the gold surface further enables systematic investigations of twist-angle-dependent electronic properties in TMD-gold heterostructures.

STM measurements reveal strong substrate-induced hybridisation, leading to substantial modification of the intrinsic electronic structure. Monolayer MoS₂ exhibits metallic behaviour with twist-angle-dependent moiré modulations of the band edges, governed primarily by spatially varying interfacial hybridisation. In monolayer VSe₂, coupling to gold suppresses the charge density wave phase, which re-emerges in bilayer or locally decoupled regions. These results highlight the role of interfacial coupling and twist angle in influencing the electronic properties of two-dimensional materials. In addition, we also identified the fundamental limitations of geometric phase analysis in moiré systems, demonstrating that delusive periodic strain can arise even in the absence of true lattice distortion.