A theoretical investigation of the modulational instability (MI) of dust–acoustic waves (DAWs) by deriving a nonlinear Schrodinger equation in an electron-depleted opposite polarity dusty plasma system containing non-extensive positive ions is presented. The conditions for MI of DAWs and formation of envelope solitons are investigated. The sub-extensivity and super-extensivity of positive ions are seen to change the stable and unstable parametric regimes of DAWs. The addition of dust grains causes changes the width of both bright and dark envelope solitons. The findings of this study can help understanding the nonlinear features of DAWs in Martian atmosphere, cometary tails, solar system, laboratory experiments, etc.