Glutathione transferases (GSTs) are multifunctional enzymes that play important roles in plant development and responses to biotic and abiotic stress. However, a systematic analysis of GST family members in Brassica napus has not yet been reported. In this study, we identified 179 full-length GST genes in B. napus, 44.2% of which are clustered on various chromosomes. In addition, we identified 141 duplicated GST gene pairs in B. napus. Molecular evolutionary analysis showed that speciation and whole-genome triplication played important roles in the divergence of the B. napus GST duplicated genes. Transcriptome analysis of 21 tissues at different developmental stages showed that 47.6% of duplicated GST gene pairs have divergent expression patterns, perhaps due to structural divergence. We constructed a GST gene coexpression network with genes encoding various transcription factors (NAC, MYB, WRKY and bZIP) and identified six modules, including genes expressed during late seed development (after 40 days; BnGSTU19, BnGSTU20 and BnGSTZ1) and in the seed coat (BnGSTF6 and BnGSTF12), stamen and anther (BnGSTF8), root and stem (BnGSTU21), leaves and funiculus, as well as during the late stage of pericarp development (after 40 days; BnGSTU12 and BnGSTF2) and in the radicle during seed germination (BnGSTF14, BnGSTU1, BnGSTU28, and BnGSTZ1). These findings lay the foundation for elucidating the roles of GSTs in B. napus.