Photoinitiators are used in the curing process during UV printing of food carton labels. The alarm concerning the detection of a photoinitiator, 2-isopropyl thioxanthone (ITX), in food samples packed with cartons printed with UV-cured inks has focused the attention of legislative authorities on the potential migrants from packaging inks into foods. For this reason it is very important to carry out analytical methods for the detection of those compounds in food as potential migrants from packaging. The aim of the present work was to develop a multimethod for the analysis of 6 photoinitiators in milk. The selected photoinitiators were Irgacure 184, benzophenone, Irgacure 651, Irgacure 907, Quantacure ITX, and Quantacure EHA (2-ethylhexyl-4-dimethylaminobenzoate). Milk (10 mL) extraction was carried out by using ammoniac and hexane. The supernatant was evaporated and the residue was redissolved with acetonitrile. Then, the extract was analyzed by HPLC-UV. Calibration lines were carried out over the concentration range of 0.1 to 10 mg/L. The calibration data presented high correlation coefficients (>0.9999). Mean recoveries (n = 6) of the 6 photoinitiators were 83.4% (residual standard deviation = 2.3%) at 0.5 mg/kg and 81.0% (residual standard deviation = 4.6%) at 1 mg/kg. Several milk samples and their respective packaging cartons were analyzed. Results were confirmed by HPLC-mass spectrometry.