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This study aims to describe the nicotine metabolite ratio among tobacco smokers and electronic cigarette (e-cigarette) users and nonusers. We analyzed pooled data from a longitudinal and a cross-sectional study of the adult population from the city of Barcelona. The final sample included information on 166 smokers, 164 e-cigarettes users with nicotine, 41 e-cigarette users without nicotine, 95 dual users (users of both products), and 508 nonusers. We used log-linear models to control for the potential confounding effect of the daily number of cigarettes smoked. Salivary nicotine metabolic rate assessment included the rate of nicotine metabolism (cotinine/nicotine) and the nicotine metabolite ratio (trans-3′-hydroxycotinine/cotinine). Exclusive users of e-cigarette without nicotine have the lowest rate of nicotine metabolism (Geometric mean: 0.08, p-values < 0.001) while cigarette smokers have the highest (Geometric mean: 2.08, p-values < 0.001). Nonusers have lower nicotine metabolic rate than cigarette smokers (Geometric means: 0.23 vs. 0.18, p-value < 0.05). Younger individuals (18−44 years) have a higher rate of nicotine metabolism than older individuals (45−64 years and 65−89) (Geometric means: 0.53 vs. 0.42 and 0.31, respectively, p-values < 0.01) and individuals with lower body mass index (21−25 kg/m2) have a higher rate of nicotine metabolism than the rest (26−30 kg/m2 and 31−60 kg/m2) (Geometric means: 0.52 vs. 0.35 and 0.36, respectively-values < 0.01). Nicotine metabolic rates are useful biomarkers when reporting smoking status and biological differences between individuals.