The plane strain fracture toughness of polyphenylene sulfide (PPS), tested with different molecular structures such as linear PPS, heat-treated PPS, and branched PPS, was investigated over a wide range of melt viscosity and crystallinity and compared with other mechanical properties. The fracture toughness of linear PPS increased with increasing melt viscosity, and it reached the highest fracture toughness calculated from linear elastic fracture mechanics (LEFM) observed in this study. In this high melt viscosity region, the linear PPS specimen showed slow crack growth instead of brittle fracture. Although the tensile properties of heat-treated PPS and branched PPS are the same as those of linear PPS, the fracture toughness of linear PPS is superior. The fracture toughness is affected by the crystallinity of the specimen, and the effect of crystallinity on fracture toughness is smaller than that of melt viscosity and molecular structure.