Uridine diphosphate glucose dehydrogenases (UGDHs) are critical for synthesizing many nucleotide sugars and help promote the carbohydrate metabolism related to cell wall synthesis. In plants, UGDHs are encoded by a small gene family. Genome-wide analyses of these genes have been conducted in Glycine max and Arabidopsis thaliana, however, the UGDH gene family has not been comprehensively and systematically investigated in moso bamboo (Phyllostachys edulis), which is a special woody grass monocotyledonous species. In this study, we identified nine putative PeUGDH genes. Furthermore, analysis of gene duplication events and divergences revealed that the expansion of the PeUGDH family was mainly due to segmental and tandem duplications approximately 4.76-83.16 million years ago. An examination of tissue-specific PeUGDH expression indicated that more than 77% of the genes were predominantly expressed in the stem. Based on relative expression levels among PeUGDH members in different tissues in moso bamboo, PeUGDH4 was selected for detailed analysis. The results of subcellular localization indicated that PeUGDH4-GFP fusion proteins was observed to be localized in the cytoplasm. The ectopic overexpression of PeUGDH4 in Arabidopsis significantly increased the contents of hemicellulose and soluble sugar, suggesting that PeUGDH4 acts as a key enzyme involved in bamboo cell wall synthesis.