An investigation has been conducted on burn ligaments, addressing the specific conditions in burn arising from dehydration and heating, and how these affect the structure-property relationship of collagen for reinforcing the tissue. Collagen fibres were isolated from a sheep’s anterior cruciate ligament, i.e. our model for this study, and divided into six groups. The first group was designated as control; the second (D) group was dehydrated without exposure to elevated temperature. The remaining (DH) groups were dehydrated followed by heating at 120oC for 30 minutes, 2, 4 and 24 hours, respectively. Tensile test to rupture was carried out to derive the fibre modulus of elasticity (E), maximum stress (σ), strain at maximum stress (ε) and strain energy density to maximum stress (u). Electron micrographs of the ruptured ends reveal a mixed mode of fibril pull-out and rupture: fibril pull-out dominates in the control group but fibril rupture dominates increasingly in the other groups, i.e. with increasing exposure time to elevated temperature. Apart from ε, there is significant increase in E, σ and u in the D and DH groups with respect to the control group but there is no evidence of variation among the D and DH groups. The results of this study implicate (1) the removal of water in the hydrated proteoglycan-rich matrix, leading to shrinkages at micrometer length-scale during dehydration, and (2) the alteration of the collagen organisation arising from the underlying changes in the crystallinity and denaturation during heating, on the mechanical properties of burn collagen fibres.