The material behavior of ligament is determined by its constituents, their organization and their interaction with each other. To elucidate the origins of the multiaxial material behavior of ligaments, we investigated ligament response to shear loading under both quasi-static and rate-dependent loading conditions. Stress relaxation tests demonstrated that the tissue was highly viscoelastic in shear, with peak loads dropping over 40% during 30 min of stress relaxation. The stress relaxation response was unaffected by three decades of change in shear strain rate (1.3, 13 and 130%/s). A novel parameter estimation technique was developed to determine material coefficients that best described the experimental response of each test specimen to shear. The experimentally measured clamp displacements and reaction forces from the simple shear tests were used with a nonlinear optimization strategy based around function evaluations from a finite element program. A transversely isotropic material with an exponential matrix strain energy provided an excellent fit to experimental load–displacement curves. The shear modulus of human MCL showed a significant increase with increasing shear strain (p<0.001), reaching a maximum of 1.72±0.4871 MPa. The results obtained from this study suggest that viscoelasticity in shear does not likely result from fluid flow. Gradual loading of transversely oriented microstructural features such as intermolecular collagen crosslinks or collagen-proteoglycan crosslinking may be responsible for the stiffening response under shear loading.