We report a highly regioselective 1,2-addition of P(O)-H compounds to the in situ generated β,γ-alkynyl-α-ketimine derived from 3-alkynyl-3-hydroxyisoindolinones, which provided a general protocol for the preparation of 3,3-disubstituted isoindolinones featuring both phosphoryl and alkynyl groups at a quaternary carbon center. The use of only 2-5 mol % of an inexpensive catalyst (In(ClO4)3·8H2O or Bi(OTf)3) allowed the smooth output of the desired products under mild conditions (25 °C, 0.5-24 h) with a broad substrate scope (35 examples) in up to >99% yield. The obtained products could be further elaborated based on the alkyne moiety. The initial asymmetric trial indicated that the use of BINOL-derived CPA could enable an enantioselective induction in up to a 46% yield with 77% ee.