The Western Ghats (WG), with an average elevation of ~1.2 km, is one of the greatest escarpments that spans ~1500 km parallel to the west coast of India. It is a mosaic of disparate geological formations having distinct structural and physical characteristics. In this study, the lithospheric structure in terms of crustal thickness, sub-Moho layer and deformation along and across the WG are investigated using receiver functions (RFs) at 30 broadband seismological stations. Techniques like slant stacking, common conversion point imaging and harmonic decomposition are applied to the RFs. Results reveal a large crustal thickness of ~45 km in the central part of the WG, which decreases to ~39 km in the southern and ~ 37 km in the northern parts, in conformity with the geology. The variation in crustal thickness beneath the WG could be due to the effect of hotspot impingement and subsequent rifting mechanism. Further, the RFs reveal a strong sub-Moho low velocity layer (LVL) along the WG. This observation gains support from a previous inference of a low-density zone in the uppermost mantle beneath the west coast of India. Harmonic decomposition of the RFs reveals that this LVL is anisotropic, while the Moho is dipping/ anisotropic in nature. The trend of the symmetry axis of anisotropy (of the LVL) varies from 58.2∘ to 134.4∘, almost perpendicular to the west coast of India. We postulate that the origin of this LVL can be linked to different rifting episodes along the west coast of India, since LVLs are manifestations of thermal/chemical anomalies. These results support the rifting model proposed for the evolution of WG.