A photoactive difluoroborate-based conjugated organic polymer (B-COP) with A(3)B(2)-type donor-acceptor arrays in the polymer framework was synthesized by direct polycondensation and exhibited amorphous structure, high thermal and photophysical stability. The B-COP was shown to be a highly efficient heterogeneous photocatalyst for a wide range of photocatalytic transformations, including the oxidative coupling of primary amine and cross-dehydrogenative coupling reactions between tetrahydroisoquinolines and nucleophiles such as nitromethane, nitroethane, acetone and phenylethyl ketone.