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
⊗
π
B
)
-invariant quantum states are separable if and only if all extremal unital positive
(
π
B
,
π
A
)
-covariant maps are decomposable where
π
A
,
π
B
are unitary representations of a compact group and π
A
is irreducible. Moreover, an extremal unital positive
(
π
B
,
π
A
)
-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
)
=
a
Tr
(
ρ
)
d
Id
d
+
b
ρ
+
c
ρ
T
+
(
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).