AbstractMatrix‐assisted laser desorption/ionization (MALDI) in combination with mass spectrometry proved to be a viable method for identifying additives in polyethylene ex tracts. The MALDI mass spectra of additives standards were found to be very simple consisting of [M+H]+and/or [M+Na]+pseudo molecular ions with little fragment ions. For real samples, which of ten contain more than one additive, the production of only one or two ions for each additive makes the tentative assignment much easier. Collision induced dissociation (CID) of the pseudomolecular ion is used to confirm the tentative assignment. The analysis of highmolecular weight additives, such as Chimassorb 944 and Tinuvin 622 indicated that MALDI was superior to other ionization techniques such as electrospray ionization (ESI), desorption chemical ionization (DCI) and fast atom bombardment (FAB) in the analysis of high molecular weight polymer additives. Sample preparation was found to be more critical than DCI in the analysis of real sample. The signals were interfered by the low molecule weight polyethylenemolecules, which were co‐extracted with the additives. This problem was partially overcome by using acetone in stead of methanol to precipitate the low molecular weight polyethylenemolecu