Herein we describe a general visible-light-induced catalyst-free protocol that enables deoxygenative alkylation of N-sulfinyltritylamine with alcohols via xanthate salts for the construction of various sulfinamides. Compared to previous works, our approach features simple operation, avoiding use of photocatalyst, broad substrate scope (including primary, secondary, and tertiary alcohols), and postmodification of natural products and drugs. Additionally, preliminary mechanistic studies suggest that this reaction undergoes a radical pathway, and an EDA complex formation between PnBuAd2 and N-sulfinyltritylamine is the key for its success.