A new Ni(II)-α-diimine-based porous organic polymer, namely Ni(II)-α-diimine-POP, was constructed in high yield via the Sonogashira coupling reaction between the metallo-building block of Ni(II)-α-diimine and 1,3,5-triethynylbenzene. Besides the high thermal and chemical stability, the obtained Ni(II)-α-diimine-POP can be a highly active reusable heterogeneous catalyst to promote the Suzuki–Miyaura coupling reaction. The obtained results indicate that the Ni(II)-α-diimine-POP herein is a promising sustainable alternative to the Pd-based catalysts for catalysing the C–C formation in a heterogeneous way.