Formulated lubricants correspond to high value products used for several applications in automotive, industrial, medicinal, and agro-food sectors. They correspond to complex matrices composed of approximately 80% of base oils (mineral or synthetic) and of about 20% of additives. Additives are generally low molecular weight polymeric molecules with a great diversity of elements. To characterize such complex compositions at the molecular level, ultrahigh resolution mass spectrometers are required. Two formulated lubricants and two additive packages were analyzed by Fourier transform ion cyclotron resonance mass spectrometry in direct infusion. Atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) sources were used to have an exhaustive characterization of the samples. The Kendrick mass defects (KMD) plot is a widespread representation to characterize polymeric molecules. Here, the terms apparent mass defect and apparent Kendrick mass defects (aKMD) values were introduced to consider the uncertainty on nominal mass determination. Several additive families including alkyldiphenylamines, trisalkylphenylthiophosphoric acid, zinc dithiophosphates, bisuccinimide dispersants, and their derivatives were observed by APCI(+). ESI(-) also presented a use for the selective ionization of acidic compounds including sulfonates, phenates, and sulfur phenate molecules. The specific aKMD values and polydispersity of many additive families have been reported to create a database of additives. Overall, this study demonstrated the great utility of the aKMD approach and the use of the ESI/APCI combination for a simple and fast characterization of formulated lubricant and additive package samples.