The Barriers to Cessation Scale (BCS; Macnee & Talsma, 1995a) was developed to assess global and specific perceived barriers that may interfere with the quit process. Although the BCS is widely used in the literature, little scientific work has been devoted to examining the psychometric properties of the measure. Thus, the present study sought to address this gap by evaluating the BCS in a sample of 497 treatment-seeking smokers. The current study examined the factor structure of the BCS, measurement invariance of the BCS subscales across sex and over 2 time points, and evaluated construct validity. Results indicated that the BCS was best modeled by a higher order factor structure wherein the originally proposed 3-factor solution (Addiction, External, and Internal) constituted the lower order and a global factor constituted the higher order factor. The higher order BCS structure demonstrated partial measurement invariance across sex and full measurement invariance from baseline to quit day among treatment seeking smokers. Additionally, expected relations were observed between the BCS subscales and similar and divergent constructs, and predictive validity was partially supported. The current findings provide novel empirical evidence that the BCS is a reliable measure of perceived barriers to smoking cessation across multiple domains and is related to several affective and smoking processes the may interfere with the process of quitting.