Sunscreens are aimed at protecting skin from solar ultraviolet (UV) irradiation. By utilizing femtosecond transient absorption spectroscopy and time-dependent density functional theory, we explain nature's selection of sinapoyl malate rather than sinapic acid as the plant sunscreen molecule. In physiological pH conditions, the two molecules are deprotonated, and their excited ππ* states are found to relax to the ground states in a few tens of picoseconds via a barrierless trans-cis photoisomerization. After the cis-photoproduct is formed, the efficacy of sinapic acid is greatly reduced. In contrast, the efficacy of sinapoyl malate is affected only slightly because the cis-product still absorbs UV light strongly. In addition, protonated sinapic acid is found to be a good potential sunscreen molecule.