In pulsed laser drilling, melt ejection greatly influences the keyhole shape and its quality as well, but its mechanism has not been well understood. In this paper, numerical simulation and experimental investigations based on 304 stainless steel and aluminum targets are performed to study the effects of material parameters on melt ejection. The numerical method is employed to predict the temperatures, velocity fields in the solid, liquid, and vapour front, and melt pool dynamics of targets as well. The experimental methods include the shadow-graphic technique, weight method, and optical microscope imaging, which are applied to real-time observations of melt ejection phenomena, measurements of collected melt and changes of target mass, observations of surface morphology and the cross-section of the keyhole, respectively. Numerical and experimental results show that the metallic material with high thermal diffusivity like aluminum is prone to have a thick liquid zone and a large quantity of melt ejection. Additionally, to the best of our knowledge, the liquid zone is used to illustrate the relations between melt ejection and material thermal diffusivity for the first time. The research result in this paper is useful for manufacturing optimization and quality control in laser-material interaction.