The invention relates to a detection method of determining 16 types of photoinitiators in a paper printing and packaging material, which is used for determining residual amounts of the 16 types of photoinitiators of 2-hodroxy-2-methyl-1-phenylacetone, mehtyl phenylglyoxylate, benzophenone and the like and is characterized by comprising the following concrete steps of: a, sample pretreatment; b, preparation of a standard work solution; c, instrumental analysis; and d, result calculation. Compared with the prior art, through sample pretreatment and optimization of instrumental analysis conditions, the detection method has the advantages that efficiency is high, the 16 kinds of photoinitiators can be simultaneously analyzed and determined within 25m; and printing ink impurities in a sample extraction solution can be better removed in a liquid-liquid distribution impurity removal mode adopted in the sample pretreatment process, so that cost is low, consumption is little, efficiency is high, and sensitivity is high; and in addition, the detection method also has the advantages of high accuracy and good repeatability.