Psychic Maws are type of normal Maws added in the Wrath of the Lamb DLC for the original game, and also appear in the Rebirth remake. They will rarely replace regular Maws and Red Maws.
Both their eyes and mouth are stitched shut, with a large third eye burning with purple flames on their forehead, which is crying with blood.
Behavior

Psychic Maw from the original game.
They behave exactly like other Maws, but fire large, purple homing shots, thus making them a much greater threat. They also have an Eternal Fly orbiting them, which can block Isaac's tears.
Its large homing shot only deals half a heart damage.
Eternal Champion Behavior
Eternal Psychic Maw behaves exactly like its normal counterpart, but has 3 Eternal Flies orbiting itself.