The success of an invasive species depends in part on its niche and the new niche opportunities that such species may find in the invaded habitat. Niche opportunities can be understood as the potential provided by a community to an invasive species to expand its niche by changes in habitat use, behavior, or diet, that favors population growth, reflected in the species occupying more habitat. This may occur under a favorable combination of access to resources that can be further favored by a lack of competitors and a release from natural enemies. The American mink (Neovison vison) is a crepuscular/nocturnal and semi-aquatic mustelid native to North America that generally concentrates activities at <100 m from the water. It has recently established an invasive population on Navarino Island in southern Chile. Here, the mink is now the top terrestrial predator free of predators or competitors. We hypothesized that this lack of potential predators and competitors, together with a more diurnal and terrestrial prey, have resulted in the mink expanding its spatial and temporal niche on Navarino Island as compared to that in its native habitats, expressed in occupancy of sites away from water and diurnal activity. We evaluated this by using 93 randomly-chosen camera-trap stations, occupancy models and mink daily activity patterns. Models showed a dynamic occupancy with the area occupied by mink being highest during summers and lowest in spring with seasonal changes in occupancy related to distance to water sources. Mink occupied and were active at sites up to 880 m from water sources during summers. Occupancy decreased at shorter distances from water during spring, but mink were still active at up to 300 m from water. Mink were active daylong during summers, and nocturnal and crepuscular during winter and spring. These results show that compared to the native and other invaded habitats, on Navarino Island mink use more terrestrial habitats and are more diurnal during summers, suggesting a niche expansion under new niche opportunities that may enhance the negative impacts of this predator on a myriad of small native vertebrates.