Large amounts of polychlorinated dibenzo-p-dioxin and furans (PCDD/F), polychlorinated biphenyls (PCB) and polychlorinated benzenes (PCBz) were formed by de novo synthesis using model ashes. The de novo synthesis was affected by SO2 and H2O. Knowledge of congener pattern and homologue profiles of PCDD/F, PCB and PCBz is help for elaborating the mechanism of formation and influence of the toxic compounds formed by de novo synthesis. By the help of the component analysis (CA) the best correlated congeners are effectively detected. Various good correlated pairs between PCDD/F, PCB and PCBz have been elaborated by using linear regression between the 15 samples. It was found that a good correlation between PCBz and PCDF.