This work aimed to develop and propose methods for evaluating the metal degree of liberation to characterize the metal deportment/concentration and liberation/association of mechanically processed waste Printed Circuit Boards (PCBs) that hold the complex and heterogeneity structure and metal distribution/association. Waste PCBs passed through a series of mechanical processing (i.e. comminution, sieving) for the metal recovery were characterized to understand and to evaluate the metal distribution and degree of liberation of the metals in order to optimize the comminution process, avoiding excessive fine particle production. The characterizations were performed at laboratory scale, as well as utilizing large scale experimental facilities, i.e. a portable X-Ray Fluorescence (XRF), micro-XRF and Synchrotron X-Ray Tomography. The proposed methods confirmed that metal liberation was very high in the fine size fraction (0.125–0.350 mm) while many locked particles were identified in the coarse size fraction (0.350–0.500 mm). Such results were analyzed and were discussed in order to better understand metal deportment/concentration behaviors. The advantages and disadvantages related to the different characterization approaches were identified and discussed in this paper, as well as their methodological developments in a waste PCBs’ mechanical processing perspective.