We developed a rhodium-catalyzed chain-walking hydrothiolation process for internal alkenes, which offers a novel and efficient alternative for C(sp3)-H bond cleavage, while focusing on thiol incorporation. This method exclusively affords N,S-acetals at 36-90% yields. Regioconvergent hydrothiolation significantly improved the effectiveness of this transformation. Preliminary mechanistic investigations revealed that an amide-directing group is essential for regioselective synthesis, underlining its significance in this process.