In the present study, 2D Co(II) coordination polymers (CP-1), which integrate terminal CoBr n (CoBr 2 and CoBr 3 ) sites immobilized on the framework, are synthesized at the gram level. As a special heterogeneous catalyst, CP-1 shows regioselectivity (β:α > 99:1) and stereoselectivity (only E configuration) in the hydroboration of alkynes. The hydroboration reaction conditions are mild and cover a broad substrate range (31 examples). In addition, the heterogeneous catalyst can be recycled for at least five times.