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Nickel(II) dichloride complexes with a pyridine-chelated imidazo[1,5-<i>a</i>]pyridin-3-ylidene py-ImPy ligand were developed as novel catalyst precursors for acrylate synthesis reaction from ethylene and carbon dioxide (CO₂), a highly promising sustainable process in terms of carbon capture and utilization (CCU). Two types of ImPy salts were prepared as new C,N-bidentate ligand precursors; py-ImPy salts (<b>3</b>, <b>4a</b>–<b>4e</b>) having a pyridine group at C(5) on ImPy and a <i>N</i>-picolyl-ImPy salt (<b>10</b>) having a picolyl group at N atom on ImPy. Nickel(II) complexes such as py-ImPyNi(II)Cl₂ (<b>7</b>, <b>8a</b>–<b>8e</b>) and <i>N</i>-picolyl-ImPyNi(II)Cl₂ (<b>12</b>) were synthesized via transmetalation protocol from silver(I) complexes, py-ImPyAgCl (<b>5</b>, <b>6a</b>–<b>6e</b>) and <i>N</i>-picolyl-ImPyAgCl (<b>11</b>). X-ray diffraction analysis of nickel(II) complexes (<b>7</b>, <b>8b</b>, <b>12</b>) showed a monomeric distorted tetrahedral geometry and a six-membered chelate ring structure. py-ImPy ligands formed a more planar six-membered chelate with the nickel center than did <i>N</i>-picolyl-ImPy ligand. py-ImPyNi(II)Cl₂ complexes (<b>8a</b>–<b>8e</b>) with <i>tert</i>-butyl substituents exhibited noticeable catalytic activity in acrylate synthesis from ethylene and CO₂ (up to 108% acrylate). Interestingly, the use of additional additives including monodentate phosphines increased catalytic activity up to 845% acrylate (TON 8).