A feasibility study for the continuous formation of multi-layer graphene (MLG) on both through-Si-via (TSV) top surface and all through the TSV sidewall and the bottom surface of high-aspect-ratio TSV by thermal chemical vapor deposition (CVD) technique has been carried out. Both microstructural and μ-Raman studies on cross-sectional graphene-TSV samples confirmed that the continuous formation of MLG all along the TSV side wall for the CVD growth temperatures of 650°C and above, and it may be used as thermal TSVs for heat removal in the stacked tiers of 3D-LSI/IC.