Abstract Introduction Australian workers’ daily tobacco smoking over time was examined by industry and occupation, to identify factors associated with high and/or low prevalence. Aims and Methods Secondary analyses of 2007, 2010, 2013, and 2016 National Drug Strategy Household Surveys were undertaken (pooled n = 49 395). Frequency analyses informed subsequent modeling of select industries and occupations. Four logistic regression models estimated adjusted effects of demographics on daily smoking in industries with high (≥20%) and low (≤15%) daily smoking prevalence and occupations with high (≥20%) and low-moderate (<20%) daily smoking prevalence. Results The sample comprised 55.7% men, 34.1% 25–39-year-olds, 31.4% New South Wales residents, 70.1% metropolitan residents, 66.9% high socioeconomic status workers, and 70.6% with low psychological distress. Daily smoking prevalence differed by industry and occupation in 2007, generally decreasing between 2007 and 2016. In high prevalence industries, daily smoking was associated with male gender and age (25–39-year-olds) and in low prevalence industries with males and nonmetropolitan workers. In high prevalence occupations, daily smoking was associated with males, female nonmetropolitan workers, and age 25–39 years and in low-moderate prevalence occupations with nonmetropolitan workers and negatively associated with females aged 14–24 years. In all models, increased odds of daily smoking were associated with low socioeconomic status and very high psychological distress. Conclusions Low socioeconomic status and very high psychological distress were risk factors for daily smoking regardless of industry, occupation, or high preexisting smoking prevalence. Targeted, as well as universal, interventions are required for workplaces and workers with greatest smoking vulnerability and least smoking cessation progress. Implications Specific strategies are warranted for identified industries, occupations, and subgroups with increased odds of daily tobacco smoking. Industries and occupations with low-moderate smoking prevalence may confer workers some protection but are not without risk; some subgroups in these settings (eg, nonmetropolitan areas) had elevated daily smoking risk. Hence, the following are supported: (1) universal interventions directed at low socioeconomic workers and workers with very high psychological distress regardless of workplace; (2) interventions targeted at high prevalence industries; (3) cessation efforts targeted for young workers in high prevalence industries and occupations; and (4) focused interventions addressing specific needs of nonmetropolitan at-risk workers in low prevalence industries.