Cigarette smoking might accelerate cognitive impairment; however, this has never been investigated using human cerebrospinal fluid (CSF). We conducted this study to investigate the association between cigarette smoking and cognitive impairment through metal ions in CSF. We obtained 5-ml CSF samples from routine lumbar puncture procedures in patients undergoing anterior cruciate ligament reconstruction before surgery in China. A total of 180 Chinese males were recruited (80 active smokers and 100 non-smokers). We measured specific cigarette-related neurotoxic metal ions in CSF, including iron, copper, zinc, lead, aluminum, and manganese. Sociodemographic data and history of smoking were obtained. The Montreal Cognitive Assessment (MoCA) was applied. Active smokers had fewer years of education (11.83 ± 3.13 vs. 13.17 ± 2.60, = 0.01), and higher age (33.70 ± 10.20 vs. 29.76 ± 9.58, = 0.01) and body mass index (25.84 ± 3.52 vs. 24.98 ± 4.06, =0.03) than non-smokers. Compared to non-smokers, active smokers had significantly higher CSF levels of iron, zinc, lead, and aluminum and lower MoCA scores (all < 0.05). Average daily numbers of cigarettes smoked negatively correlated with the MoCA scores ( = -0.244, = 0.048). In young smokers, CSF manganese levels negatively correlated with MoCA scores ( = -0.373, = 0.009). Cigarette smoking might be associated with male cognitive impairment, as shown by lower MoCA scores and higher levels of CSF iron, zinc, lead, and aluminum in active smokers. This might be early evidence of cigarette smoking accelerating male cognitive impairment.