Our previous studies of raspberry-like carbon black/polystyrene (CB/PS) composite particles suggested that their morphologies could be tailored as the coverage degree of CB on PS microspheres. Morphologies of these composite particles were investigated by scanning electron microscope. The CB/PS composites prepared by using raspberry-like CB/PS particles had lower percolation threshold than that of general CB/PS composites. Optical microscopy photographs indicated that hierarchical structure of composite particles enabled CB particles to form more effective networks within the matrix. Raspberry-like structure dispersed CB particles in the interfaces between polycarbonate (PC) and PS when CB/PS particles were introduced into PC as additives. The effects of concentration of PS, coverage degree of CB, and concentration of CB on electrical properties of CB/PS/PC composite were investigated. The results showed that the percolation threshold of CB/PS/PC composite was improved when PS concentration was at the range of 20-80% and coverage degree of CB was more than 5% simultaneously.