A solvent-controlled unprecedented tandem reaction of readily accessible SeO2, a wide variety of sulfonyl hydrazides, and alkynes has been established for the chemodivergent construction of structurally complex 1,2-bis((E)-1-aryl-2-arylsulfonylvinyl)diselanes and bis((E)-1-aryl-2-(arylsulfonyl)vinyl)selanes via a catalyst-free one-pot three-component approach, respectively. The adjustable and controlled synthetic strategy shows good yields and chemoselectivities for most substrates under mild and simple conditions.