Tissue-level stress-relaxation of ligaments and tendons in the toe region is characterized by fast and long-term relaxations and an increase in relaxation magnitude with strain. Characterizing the compositional and structural origins of these phenomena helps in the understanding of mechanisms of ligament and tendon function and adaptation in health and disease. A three-step tensile stress-relaxation test was conducted on dumbbell-shaped pieces of bovine knee ligaments and patellar tendon (PT) ( n = 10 knees). Their mechanical behaviour was characterized by a fibril-reinforced poroviscoelastic material model, able to describe characteristic times and magnitudes of fast and long-term relaxations. The crimp angle and length of tissues were measured with polarized light microscopy, while biochemical contents were determined by colorimetric biochemical methods. The long-term relaxation time was longer in the anterior cruciate ligament (ACL) and PT compared with collateral ligaments ( p < 0.05). High hydroxyproline content predicted greater magnitude and shorter time of both fast and long-term relaxation. High uronic acid content predicted longer time of long-term relaxation, whereas high crimp angle predicted higher magnitude of long-term relaxation. ACL and PT are better long-term stabilizers than collateral ligaments. The long-term relaxation behaviour is affected or implied by proteoglycans and crimp angle, possibly relating to slow structural reorganization of the tissue.