Herein, by applying visible-light photoredox catalysis, we have now achieved the first example of catalytic dehydrogenative coupling of phosphines and thiophenols that proceeds at room temperature. Key to our success is the use of benzaldehyde as a soft oxidant, which avoids the issue of phosphine oxidation. Furthermore, we observed the unexpected dealkylative coupling of secondary and tertiary alkylphosphine with thiophenols.