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The aim of our study was to estimate the association of cigarette smoking with burnout syndrome in medical students at the University of Kragujevac, Serbia. Burnout syndrome is defined as a triad of symptoms: emotional exhaustion, cynicism, and academic inefficiency. Cigarette smoking was significantly associated with cynicism, with smokers often showing higher cynicism compared to non-smokers (40.7% vs. 32.3%; <i>p</i> = 0.023). Additionally, cigarette smoking was significantly associated with higher academic inefficiency, with smokers often showing academic inefficiency compared with non-smokers (43.6% vs. 35.0%; <i>p</i> = 0.022). Cigarette smoking was not significantly associated (44.9% vs. 38.5%; <i>p</i> = 0.096) with emotional exhaustion.