Background: Maternal smoking during pregnancy and parental offending are both linked to adverse offspring outcomes. Few studies have examined how these exposures together influence diverse offspring outcomes in early childhood. Aims: To examine associations between quantity of prenatal maternal smoking and frequency of maternal offending and offspring behavioural and cognitive outcomes at age 5 years. Methods: Over 66,000 Australian children (mean age 5.6 years) were drawn from an intergenerational data linkage study. Unadjusted and adjusted logistic regressions were conducted for the two key exposures (maternal prenatal smoking and mother having at least two criminal convictions) and offspring behavioural and cognitive vulnerabilities. Population attributable fractions (PAFs) were also estimated for each outcome for the two exposures. Results: Prenatal smoking and maternal offending were, separately and together, associated with most of the developmental vulnerabilities examined, even after adjusting for other familial and prenatal risk factors. PAFs for prenatal smoking ranged from 5.3% to 15.8%, and PAFs for maternal offending ranged from 3.4% to 11.8% across the offspring outcomes. Conclusions: Maternal smoking during pregnancy and maternal offending were uniquely associated with a range of offspring vulnerabilities, but mothers who smoked during pregnancy tended to experience multiple problems that should also be considered as indicators of child vulnerabilities. While early behavioural difficulties were evident in these children, it was striking that they were also likely to have cognitive vulnerabilities. Early intervention to support cognitive development in these children may minimise their risk of academic underachievement, long-term disadvantage, and even offending.