Detector response of carboxylic acids (C2–C12, straight and branched chain) were investigated using a flame ionization detector (FID) in a capillary gas chromatographic system. The response of the FID for hydrocarbons is almost directly proportional to the carbon quantity introduced into the flame. Heteroatoms in the molecule reduce signal magnitude, depending on their quality and on the bond they are involved in. We expressed this reduced response with the effective carbon number (ECN). We determined the ECN contribution (ΔECN) of the carboxyl group on the alkyl skeleton. We examined how the responses of carboxylic acids change if trimethylsilyl derivatives are evaluated and we compared the ECN of the neat and derivatized form.