Selective/preferential milling of printed circuit board (PCB) particles followed by non-destructive characterization of the mill products was performed in order to understand the effects of different feed masses into a hammer mill and different milling time on the metal recovery and enrichment ratio. Those are important variables affecting and determining the process performance and capacity. The milling tests and elemental assay characterization were conducted by using a hammer mill and a portable X-ray fluorescence analysis (XRF), respectively. The results showed the preferential metal concentration/enrichment was achieved for several elements and their degree was varied depending on the parameters. Using the experimental data, predictive models of metal recovery were developed and the global trend of metal recoveries was observed under different mill feed and milling time and discussed.