This study examined the contextual factors associated with smoking initiation and cessation among women in Brazilian worksites (Curitiba, Paraná, Brazil). A total of 22 focus groups were conducted among 108 women in private and public worksites. The most frequently endorsed negative factors that contributed to smoking initiation included exposure to smoking-prompting behaviors through family members, peer pressure, media and easy access/low cost of cigarettes. Positive factors that served as protective mechanisms against initiation included smoking-related health effects and strong influence from parents and family members. The most salient negative factors associated with smoking cessation included stress/anxiety-relieving benefits, weight control, access/low cost of cigarettes, being around smokers and risk-exempting beliefs. Positive factors included smoking restrictions at home and workplace and concerns about appearance. Current and former smokers reported that they had never received any assistance from their physicians to quit smoking, nor did they rely on smoking cessation programs or aids or believe in their effectiveness. There are specific contextual factors that contribute to smoking initiation/cessation among women in Brazilian worksites which have important clinical, research and policy implications.