A simple direct titration for milligram and microgram amounts of triphenylphosphorus, -arsenic, -antimony, and -bismuth is described. The methanolic sample solution, with a little water, hydrochloric acid and bromide added, is titrated with N-bromosuccinimide to a methyl red end-point. All four compounds were titrated in the same way with recoveries of 99–100% and relative standard deviations of 1–5% were obtained.