Recycling printed circuit board waste (PCBW) waste is a hot issue of environmental protection and resource recycling. Mechanical and thermo-chemical methods are two traditional recycling processes for PCBW. In the present research, a two-step crushing process combined with a coarse-crushing step and a fine-pulverizing step was adopted, and then the crushed products were classified into seven different fractions with a standard sieve. The liberation situation and particle shape in different size fractions were observed. Properties of different size fractions, such as heating value, thermogravimetric, proximate, ultimate and chemical analysis were determined. The Rosin-Rammler model was applied to analyze the particle size distribution of crushed material. The results indicated that complete liberation of metals from the PCBW was achieved at a size less than 0.59 mm, but the nonmetal particle in the smaller-than-0.15 mm fraction is liable to aggregate. Copper was the most prominent metal in PCBW and mainly enriched in the 0.42-0.25 mm particle size. The Rosin-Rammler equation adequately fit particle size distribution data of crushed PCBW with a correlation coefficient of 0.9810. The results of heating value and proximate analysis revealed that the PCBW had a low heating value and high ash content. The combustion and pyrolysis process of PCBW was different and there was an obvious oxidation peak of Cu in combustion runs.