Chemical composition and liberation are critical attributes in characterizing a resource stock for beneficiation investigations. Though end-of-life printed circuit board is recognized as a valuable secondary resource stock, no procedural standard exists for the determination of its chemical composition, nor for the −75μm fines generated during its comminution. The effect of the digestion procedure on the final assays in wet spectroscopic analyses was assessed in this work. Liberation was also explored against literature background. Determination of assays of all constituent elements in printed circuit board comminution fines was found to require comparison of data from more than one digestion condition, while composite particles still persist at the fines sizes, though very few. The discussion reflects how these impact the beneficiation investigations.