A photocatalytic C−H disulfuration of indolizines was developed, giving an approach to a wide variety of indolizine-3-disulfides with good yields. Trisulfide dioxides were explored as a high-efficient disulfuration reagent. This disulfuration reaction could be scaled up to grams. Mechanistic studies support a photoinduced pathway involving the generation of indolizine cationic radicals. A bulky alkyl substituent on terminal sulfur of trisulfide dioxide A was necessary for selective formation of disulfide over monosulfide.