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Objectives. The association between platelet distribution width (PDW) and mortality in hemodialysis (HD) patients has received little attention. Methods. We retrospectively enrolled HD patients in a single center from January 1, 2008, to December 30, 2011. The primary and secondary endpoints were all-cause and cardiovascular mortality, respectively. The association between PDW and mortality was estimated by Cox regression model. Results. Of 496 patients, the mean age was 52.5 ± 16.6 years, and the Charlson comorbidity index was 4.39 ± 1.71. During the follow-up period of 48.8 ± 6.7 months, 145 patients (29.2%) died, including 74 (14.9%) cardiovascular deaths. 258 (52.0%) with PDW < 16.31% were in the low group and 238 (48.0%) in those with PDW ≥ 16.31% according to cut-off for all-cause mortality by receiving-operator characteristics. After adjusting for confounding factors, high PDW values were independently associated with higher risk of all-cause (hazards ratio (HR) = 1.49, 95% confidence interval (CI) 1.15–6.82) and cardiovascular deaths (HR = 2.26, 95% CI 1.44–3.63) in HD patients. When comparing with quartile 1 of PDW, quartile 4 of PDW was independently associated with a higher risk of all-cause (HR = 1.59, 95% CI 1.18–5.30) and cardiovascular deaths (HR = 2.71, 95% CI 1.49–3.76) in HD patients. Conclusions. Baseline PDW was independently associated with all-cause and cardiovascular mortality in HD patients.