Chlorine bleaching is still practiced by most of nonwood pulp and paper mills, resulting in a considerable amount of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) formation and emission. In this study, the effects of primary chlorination conditions on the formation of PCDD/Fs from nonwood pulp bleaching with elemental chlorine were investigated. It was found that low-chlorinated PCDD/Fs were usually formed and then underwent further chlorination to form highly chlorinated PCDD/Fs with increasing chlorination time. Higher available chlorine dosages and lower system pH values greatly accelerated dioxin formation, and pH 3 was the threshold for the formation of tetra- to octa-CDD/Fs. Higher temperatures promoted the formation of lower-chlorinated PCDD/Fs, while caused significant reduction of tetra- to hepta-CDDs and penta- to octa-OCDFs. PCDFs were formed much faster than PCDDs. A first-order kinetic model showed a good fit to the data for tetra- to oct-CDFs formation under different chlorination conditions, indicating that chlorine substitution was the rate determining step for their formation. Finally, the optimum chlorination conditions for minimizing and eliminating the formation of 2,3,7,8-TCDD/TCDF in nonwood pulp bleaching with elemental chlorine were established.