Abstract This study investigated the synergetic effect between laser beam and electrical arc during hybrid welding by using a spectral diagnostic technique. The synergetic effect increased the energy density in the keyhole and deepened the weld penetration, resulting in a lower plasma electron temperature. The metal transfer mode was a globular one at a small offset distance while a spray mode was achieved with an increase in the offset distance. The decrease in the arc voltage and arc current due to the synergetic effect caused this transition from spray to globular modes. Globular transfer mode destabilized the molten pool and keyhole with the large droplet impingement, leading to the formation of porosity in the corresponding weld bead. The presence of porosity was on-line detected by identifying serious fluctuations in the Fe I electron temperature signals based on the fact that the instability of the molten pool and keyhole is strongly related to the signals coming from the plasma.