The invention discloses a preparing method by using unactivated olefin hydrogen trifluoride methylation and application thereof. The method comprises the following steps: A, adding unactivated olefin I, sodium trifluoromethanesulfonate and a photocatalystIr[dF(CF3)ppy]2(dtbpy)PF6 into a Schlenk tube; B, vacuumizing, replacing argon, adding methyl alcohol; C, irradiating the Schlenk tube with a fluorescent lamp, and stirring to react; and D, after reaction is finished, adding water into the system to perform a quenching reaction, extracting with ethyl acetate, separating an organic phase, drying, filtering, performing rotary evaporation to remove a solvent, chromatographing the residue through an ethyl acetate / petroleum ether mixed solvent to obtain a target product II, wherein the proportion of the ethyl acetate / petroleum ether mixed solvent is selected according to different polarities of the product, and silica gel is adopted as a solid phase in column chromatography. The method applied to medicinal molecule synthesis is feasible, is simple and convenient to operate, and is used for implementing an unactivated olefin hydrogen trifluoride methylation reaction to prepare a series of trifluoromethyl-containing target compounds by selecting low-price trifluoromethyl reagent under a mild condition.