This study aimed to measure the percent agreement between Exhaled Breath Carbon Monoxide (eBCO) measure using a piCO+ smokerlyzer® and self-reported cigarette smoking status and to determine the optimal thresholds for definite identification of cigarette smokers of male school students in Jordan. A descriptive, cross sectional, study of a random sample of male adolescents in grades 7 and 8 from four public high schools in Irbid, completed an adaptation of a standardized Arabic-language tobacco smoking questionnaire and an eBCO measure. Sensitivity and specificity of the eBCO were calculated against self-reported cigarette smoking. Participants (n = 439) had a mean age of 12.5 years (SD = 0.50) and 174 (39.9%) reported being an ever smoker of whom 59 (33.9%) reported being a recent (30-day) smoker. The optimal eBCO cut-off point for recent smoking was 4.5 ppm with a sensitivity of 84.7% and specificity of 65.5%. Overall, eBCO can accurately identify recent smokers and distinguish them from non-smokers. The eBCO use enables healthcare professionals and researchers to assess efficacy of smoking cessation and prevention programs without necessarily relying on self-report. Further research is indicated to validate our findings and should be expanded to include females, detailed characteristics of cigarette and waterpipe smoking.