Background: Understanding which subgroups of vocational education students are more likely to use tobacco and/or alcohol is critical for designing interventions. Previous research has not explored important student subgroups. Objectives: This exploratory study examined tobacco use, risky alcohol consumption not meeting Australian guidelines, and concurrent use by type of vocational training and whether previously unexplored factors were associated with these health behaviors among vocational education students. Methods: A cross-sectional online survey was conducted among 1057 students (66% male) attending 14 Technical and Further Education campuses in New South Wales, Australia. Results: Type of vocational training was not associated with tobacco use, risky alcohol consumption, or concurrent use. Participants who were married/living with a partner (adjusted odds ratio (AOR): 0.69; 95% Confidence Interval (CI) 0.48, 0.99), or unemployed (AOR: 0.60; 95% CI 0.36, 0.99) had significantly lower odds of tobacco use. Indigenous students (AOR: 1.82; 95% CI 1.19, 2.80) or those who experienced symptoms of depression (AOR: 1.69; 95% CI 1.12, 2.55) had significantly higher odds of tobacco use. Participants aged ≥25 years (AOR: 0.59; 95% CI 0.40, 0.88), female (AOR: 0.42; 95% CI 0.29, 0.62), or unemployed (AOR: 0.57; 95% CI 0.37, 0.88) had significantly lower odds of risky alcohol consumption. Unemployed participants (AOR: 0.53; 95% CI 0.30, 0.95) had significantly lower odds of concurrent use. Those who experienced symptoms of anxiety (AOR: 1.55; 95% CI 1.02, 2.37) had significantly higher odds of concurrent use. Conclusion: Vocational education institutes could provide tailored and culturally appropriate interventions targeting students at increased risk of tobacco and/or alcohol use to prevent diseases.