Photoinitiators (PIs), as an important component of UV inks, are widely used in the printing of paper food packaging. Nevertheless, there is limited information concerning the identification of PIs in food packaging and their potential migration rules under natural storage condition. In this study, 23 target PIs detected in paper food packaging were dominated by benzophenones (BZPs), followed by amine co-initiators (ACIs), thioxanthones (TXs) and phosphine oxides (POs). The concentration of ΣPIs ranged between 48.3 and 1.11 × 105 ng/g. Meanwhile, the concentration of ΣPIs were found to be significantly higher in Corrugated paper compared to Polyethylene (PE) coated paper, Composite paper and White card paper. Benzophenone (BP) was found as the dominant PI congener in Corrugated paper, with the concentration ranging from 923-3.66 × 104 ng/g. The migration quantity of ΣPIs increased in a time-dependent manner in the first 13 days and then eventually reached equilibrium. Low temperatures had a certain inhibitory effect on the migration of PIs from paper packaging to food. Under high exposure scenario, the EDIs of ΣPIs for children, adolescents, and adults were 31.4 ng/(kg bw·day), 17.2 ng/(kg bw·day), and 14.4 ng/(kg bw·day), respectively, all of which did not exceed the reference dose, indicating that dietary intake of PIs does not pose any health risks to the human body.