Silver phenylacetylide prepared by one-step process was characterized as a linear coordinated polymeric compound by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectroscopy. Its prominent third-order optical nonlinearity was detected by heterodyned ultrafast optical Kerr effect (OHD-OKE) measurement. The second-order hyperpolarizability was enhanced by 2 orders of magnitude by means of incorporation of proper electron-pushing groups. The structure status was further investigated by quantum chemical calculation and molecular modeling.