Mortality was studied in a cohort of 4831 men from Estonia who participated in the environmental cleanup of the radioactively contaminated areas around Chernobyl in 1986–1991. Their mortality in 1986–2020 was compared with the mortality in the Estonian male population. A total of 1503 deaths were registered among the 4812 traced men. The all-cause standardized mortality ratio (SMR) was 1.04 (95% CI 0.99–1.09). All-cancer mortality was elevated (SMR 1.16, 95% CI 1.03–1.28). Radiation-related cancers were in excess (SMR 1.20, 95% CI 1.03–1.36); however, the excesses could be attributed to tobacco and alcohol consumption. For smoking-related cancers, the SMR was 1.20 (95% CI 1.06–1.35) and for alcohol-related cancers the SMR was 1.56 (95% CI 1.26–1.86). Adjusted relative risks (ARR) of all-cause mortality were increased among workers who stayed in the Chernobyl area ≥ 92 days (ARR 1.20, 95% CI 1.08–1.34), were of non-Estonian ethnicity (ARR 1.33, 95% CI 1.19–1.47) or had lower (basic or less) education (ARR 1.63, 95% CI 1.45–1.83). Suicide mortality was increased (SMR 1.31, 95% CI 1.05–1.56), most notably among men with lower education (ARR 2.24, 95% CI 1.42–3.53). Our findings provide additional evidence that unhealthy behaviors such as alcohol and smoking play an important role in shaping cancer mortality patterns among Estonian Chernobyl cleanup workers. The excess number of suicides suggests long-term psychiatric and substance use problems tied to Chernobyl-related stressors, i.e., the psychosocial impact was greater than any direct carcinogenic effect of low-dose radiation.