Smoking among women is characteristically high among call center employees and is associated with various individual and work-related characteristics, which have been paid little attention so far. This study explored the differences in intrapersonal and interpersonal characteristics and environmental factors among Korean women working in call centers by smoking status, based on an ecological model. In this cross-sectional study, an anonymous online survey was conducted among a sample of female employees from three credit card-based call centers (N = 588). Differences in intrapersonal (social nicotine dependence, smoking attitudes, emotional labor), interpersonal (smoking among family or friends, social support), and environmental factors (smoking cessation education, and perceived and preferred smoking policy at work) were compared according to smoking status (smokers, ex-smokers, and never smokers). Approximately 20% (n = 115) were smokers. Smokers were younger, mostly unmarried, had lower education, and had poorer perceived health status than ex- and never smokers. The mean scores for social nicotine dependence and smoking attitude were the highest among smokers, indicating their tendency to underestimate the negative effects of smoking. They also reported the highest level of emotional labor, with about half (50.4%) and almost all (95.7%) reporting smoking behaviors in their families and friends, respectively. Smokers took a lenient stance on the smoking ban policy. The results indicated the necessity to develop tailored smoking cessation programs to motivate female call center employees to quit smoking. As call centers may have a smoking-friendly environment, comprehensive smoking prevention programs considering multilevel factors are required to support smoking cessation.