A concise and elegant protocol was developed to prepare linear amines by regioselective hydroaminomethylation of terminal olefins with pyrrole-based tetraphosphorus ligands. It has been documented that the reactivity of the ligand is modulated by the substituent of the biphenylphosphane moiety. Ligand L5 containing electron-donating groups exhibited the highest reactivity, with up to 70.9 n/i ratio and 99.5% amine selectivity for 1-pentene and a 31.3 n/i ratio and 97.9% amine selectivity for 1-hexene.