Mechanical waste-processing methods, which combine crushing and separation processes for the recovery of valuable materials, have been widely applied in waste printed wiring board (PWB) treatment. However, both the high impact toughness and the tensile and flexural strengths of whole PWB with a laminated structure result in great energy consumption and severe abrasion of the cutters during multi-level crushing. In addition, the high temperatures occurring in continual crushing probably cause the decomposition of the polymer matrix. A thermal-crack method using residual steam as the heating medium has been developed to pre-treat waste PWBs. This treatment reduces the mechanical strength in order to improve the recovery rate of valuable materials in subsequent mechanical recycling. The changes of the PWBs’ macro-mechanical properties were studied to evaluate thermal expansion impacts associated with changes in temperature, and the dynamic dislocation micro-structures were observed to identify the fracture mechanism. The results showed that thermal cracking with steam at the temperature of 500 K can effectively attenuate the mechanical properties of waste PWBs, by reducing the impact, tensile and flexural strengths respectively, by 59.2%, 49.3% and 51.4%, compared to untreated PWB. Thermal expansion can also facilitate the separation of copper from glass fiber by reducing peel resistance by 95.4% at 500 K. It was revealed that the flexural fracture was a transverse cracking caused by concentrated stress when the heating temperature was less than 500 K, and shifted to a vertical cracking after exceeding 500 K.