An efficient strategy for the synthesis of unexplored 8‐quinolinesulfinate esters has been reported. The method involves in situ generation of quinoline sulfinate from N'‐acetylquinoline‐8‐sulfonohydrazide via silver mediated cleavage followed by palladium‐catalyzed cross‐coupling with 1° and 2° alcohols to yield sulfinate esters. A variety of substituted alcohols were successfully employed in the reaction. Control experiments performed to understand the mechanism, revealed that the transformation follows a radical pathway and the alcohol oxygen get incorporated in the resulting sulfinate esters. Two of the chirally pure alcohols were also used in the transformation to study the diastereoselectivity in the reaction. In order to demonstrate the synthetic utility, a representative allyl‐quinoline‐8‐sulfinate 3f was successfully converted into the 8‐(allylsulfonyl)‐quinoline 4 via palladium(II) acetate mediated isomerization.