Modulational instability of ion-acoustic waves has been theoretically investigated in an unmagnetized collisionless plasma with nonthermal electrons, Boltzmann positrons, and warm positive ions. To describe the nonlinear evolution of the wave amplitude a nonlinear Schrödinger (NLS) equation has been derived by using multiple scale perturbation technique. The nonthermal parameter, positron concentration, and ion temperature are shown to play significant role in the modulational instability of ion-acoustic waves and the formation of envelope solitons.