Salivary cotinine has been increasingly used as a biomarker to assess people's smoking status and environmental tobacco smoking exposure. Several analytic methodologies are available, ranging from point-of-care techniques to state-of-the-art laboratory-based methodologies. The features and applicability of these methods are critically addressed, regarding the chemistry involved in the cotinine determination, the required instrumental methods of analysis, and the working determination range. Considering that cotinine levels are one or two orders of magnitude lower in nonsmokers when compared to smokers, the sensitivity and the detection limit of available methods are also discussed. Finally, recent developments are presented, including mass spectrometry-based methods with minimum sample pretreatment.