In this study, the microstructure and valuable metals dissolution properties of PDP waste panel powders were investigated as a function of milling parameters such as ball diameter size, milling time, and rotational speed during high-energy milling process. The complete refinement of powder could achieved at the ball diameter size of 5 mm due to sufficient impact energy and the number of collisions. With increasing milling time, the average particle size was rapidly decreased until the first 30 seconds, then decreased gradually about at 3 minutes and finally, increased with presence of agglomerated particles of at 5 minutes. Although there was no significant difference on the size of the particle according to the rotational speed from 900 to 1,100 rpm, the total valuable metals dissolution amount was most excellent at 1,100 rpm. As a result, the best milling conditions for maximum dissolving amount of valuable metals (Mg: 375 ppm, Ag 135 ppm, In: 17 ppm) in this research were achieved with 5 mm of ball diameter size, 3min of milling time, and 1,100 rpm of rotational speed.