One of the fundamental questions in quantum information theory is determining entanglement of quantum states, which is generally an NP-hard problem. In this paper, we prove that all PPT (π―A⊗πB) -invariant quantum states are separable if and only if all extremal unital positive (πB,πA) -covariant maps are decomposable where πA,πB are unitary representations of a compact group and π A is irreducible. Moreover, an extremal unital positive (πB,πA) -covariant map L is decomposable if and only if L is completely positive or completely copositive. We then apply these results to prove that all PPT quantum channels of the form Φ(ρ)=aTr(ρ)dIdd+bρ+cρT+(1−a−b−c)diag(ρ) are entanglement-breaking, and that there is no A-BC PPT-entangled (U⊗U―⊗U) -invariant tripartite quantum state. The former strengthens some conclusions in (Vollbrecht and Werner 2001 Phys. Rev. A 64 062307; Kopszak et al 2020 J. Phys. A: Math. Theor. 53 395306), and the latter resolves some open questions raised in (Collins et al 2018 Linear Algebra Appl. 555 398–411).