Multisubstituted piperidines are prevalent units in pharmaceuticals. Herein, a photodriven anti-Markovnikov hydroaminative cyclization of a (Z)/(E)-isomeric mixture of trisubstituted alkenes using the lactate-derived C2-symmetric arylthiol catalyst was developed for the synthesis of cis-2,3-disubstituted piperidines and azepane in high diastereoselectivity and good yields. The origin of diastereoselectivity and the observed different hydroamination rate of alkene with different configurations were elucidated by the experimental and computational investigation.