Single-atom catalysts (SACs) have generated excitement for their potential to downsize metal particles to the atomic limit with engineerable local environments and improved catalytic reactivities and selectivities. However, successes have been limited to small-molecule transformations with little progress toward targeting complex-building reactions, such as metal-catalyzed cross-coupling. Using a supercritical carbon-dioxide-assisted protocol, we report a heterogeneous single-atom Pt-catalyzed Heck reaction, which provides the first C-C bond-forming migratory insertion on SACs. Our quantum mechanical computations establish the reaction mechanism to involve a novel C-rich coordination site (i.e., PtC4) that demonstrates an unexpected base effect. Notably, the base was found to transiently modulate the coordination environment to allow migratory insertion into an M-C species, a process with a high steric impediment with no previous example on SACs. The studies showcase how SACs can introduce coordination structures that have remained underexplored in catalyst design. These findings offer immense potential for transferring the vast and highly versatile reaction manifold of migratory-insertion-based bond-forming protocols to heterogeneous SACs.