Current regulations on exhaust automotive emissions focus on certain pollutants to control vehicle emissions. Hydrocarbons, the main components of gasoline, are one of these regulated compounds; however, the regulation only refers to the sum of total hydrocarbons (THC) without taking into account the individual components. Vehicles also emit a large variety of chemicals besides hydrocarbons that can become much more harmful, depending on their environmental toxicity and the amounts that are emitted to the atmosphere. In recent years, due to the emergence of alternative fuels such as bioethanol and biodiesel, the interest in these not so well characterized compounds has grown. For example, when ethanol is used in gasoline blends as a fuel for internal-combustion engine vehicles, the study of other compounds such as alcohols, aldehydes and ketones, in addition to hydrocarbons, acquires more importance. Based on SOP 101, 102-103 and 104 by California Air Resources Board (CARB), three chromatographic methods for the analysis of methanol and ethanol (HRGC-FID), aldehydes and ketones (HPLC-UV), and individual hydrocarbons (C2-C12) (thermal adsorption/desorption system-HRGC/FID-FID) have been developed. All three methods have been optimized, validated and implemented in automotive exhaust samples analysis. This has allowed us to determine regulated as well as non-regulated compounds from emissions among different ethanol-gasoline fuels (E0, E5-S, E10 and E85), applied to Euro 4 and Flexifuel vehicles.