Although there has been significant progress in the development of transition‐metal‐catalyzed hydrosilylations of alkenes over the past several decades, metal‐free hydrosilylation is still rare and highly desirable. Herein, we report a convenient visible‐light‐driven metal‐free hydrosilylation of both electron‐deficient and electron‐rich alkenes that proceeds through selective hydrogen atom transfer for Si−H activation. The synergistic combination of the organophotoredox catalyst 4CzIPN with quinuclidin‐3‐yl acetate enabled the hydrosilylation of electron‐deficient alkenes by selective Si−H activation while the hydrosilylation of electron‐rich alkenes was achieved by merging photoredox and polarity‐reversal catalysis.