A pi-acceptor phosphine-electron-deficient olefin ligand was found effective in promoting Pd-catalyzed C(sp)-C(sp) cross-coupling reactions. The new protocol realized the cross-coupling of a broad scope of terminal alkynes and haloalkynes in good to excellent yields with high selectivities. Electron-rich alkynes, which are normally difficult substrates in Glaser couplings, could be employed as either nucleophiles or electrophiles. Alkynes bearing similar substituents, such as n-C5H11CCBr and n-C4H9CCH, which usually suffer from homocoupling side reactions under Cadiot-Chodkiewicz conditions, were successfully cross-coupled in the system. Preliminary kinetic studies revealed that the reaction rate was zero-order in the concentrations of both haloalkynes and terminal alkynes and first order in the loading of Pd(dba)(2) and exhibited no obvious dependence on the loading of the copper salt. Control experiments with other phosphines such as PPh3 and DPPF as the ligand were carried out. All the kinetic evidence indicated that the phosphine-olefin ligand facilitated the reductive elimination in the catalytic cycle.