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The cover displays a selective oxidative sulfonylation of alkenes with selenium sulfonate depended on the reaction conditions. The electrochemical C—H sulfonylation proceeded smoothly to afford (E)‐vinyl sulfones with good selectivity in an undivided cell without external oxidant. While aerobic trifunctionalization of alkenes occurred in the presence of KI in the air, which provides β‐keto selenosulfones via the formation of C—O, C—S, and C—Se bonds in one‐pot. This selective synthesis is like interstellar racing, reaching distant planets from the same starting point through different paths. Following control experiments, a plausible mechanism is proposed to rationalize the experimental results. More details are discussed in the article by Cao et al. on page 1367—1372. [ABSTRACT FROM AUTHOR]