As one of the main emission sources of PCDD/Fs, the pulp and paper industry has always been public concerns. In China, the consumption of non-wood fiber as raw material of pulp accounts for a relatively larger proportion in the total productivity. Here, the unintentionally produced PCDD/Fs emissions of five Chinese non-wood pulp and paper mills were investigated. The results showed that the increment of PCDD/Fs after bleaching with chlorine was about 1.71-28.19 times in pulp and 3.96-28.82 times in wastewater based on the existing technologies. In order to reduce the unintentional production of PCDD/Fs, the BAT/BEP transformation program was proposed as cleaner production initiatives featured by less or free use of chlorine in bleaching process, and evaluated by reduction effects and costs. The study showed the application of Elemental Chlorine Free (ECF) sequences in bleaching process with improving technologies in other production stages would effectively decrease the generation of PCDD/Fs, other pollutant load as well as the water consumptions.