Early tobacco smoke exposure (TSE) in utero and/or during the first years after birth poses threats to the development of child executive functioning and self-regulation skills, including inhibitory control. Efforts are still needed to examine under what conditions such effects may occur and thus identify modifiable intervention targets. In addition, a distinction between cool and hot inhibitory control is also important to obtain greater nuance in such links. The cool inhibitory control refers to children’s suppression of prepotent automatic responses to a distracting stimulus in solving arbitrary and decontextualized problems, whereas the hot inhibitory control refers to children’s control of impulse in motivationally and emotionally high-stake situations. Using data derived from the National Institute of Child Health and Human Development Study of Early Child Care and Youth Development, we examined the links between early risk of TSE and preschoolers’ hot and cool inhibitory control and tested the potential promotive/protective roles of maternal positivity in early mother–child interactions. Results indicate that early risk of TSE was negatively linked to child cool inhibitory control when maternal positivity was low, but this link was nonsignificant when maternal positivity was high (i.e., the protective role of maternal positivity). The link between early risk of TSE and child later hot inhibitory control was not moderated by maternal positivity; instead, early risk of TSE and maternal positivity were negatively and positively associated with child hot inhibitory control above and beyond each other, respectively (i.e., the promotive role of maternal positivity). Accordingly, building a tobacco-free environment during pregnancy and infancy likely yields long-term benefits for child self-regulation development. Improving early mothering may offset the negative link between early TSE and child cool inhibitory control and also facilitate child hot inhibitory control even in the face of early TSE.