Activating small molecules is pivotal in advancing sustainable energy conversion and green chemical synthesis. Frustrated Lewis pairs (FLPs) consist of spatially separated Lewis acid and Lewis base sites, preserving the intrinsic reactivity of each site while enabling cooperative interactions that facilitate the efficient activation of small molecules. Heterogeneous FLPs, mainly by integrating FLPs onto solid supports, have been widely investigated owing to their practical advantages of high reactivity, easy separation, and stable reusability. This review comprehensively summarizes the construction methods, catalytic mechanisms, and applications of heterogeneous FLPs across various solid supports, including metal oxides/hydroxides/oxyhalides, two-dimensional (2D) carbon materials, porous frameworks, and polymers. We systematically discuss how crystal structure, surface defects, electronic properties, and elemental composition of solid supports influence the formation, spatial configuration, and reactivity of FLPs. Furthermore, the challenges in designing and investigating heterogeneous FLPs are critically highlighted, and potential avenues for future research are outlined to advance this emerging field.