Stacked-layer heterostructure films of 2D thiophene nanosheets and electrochemically exfoliated graphene are constructed for ultrahigh-rate all-solid-state flexible pseudocapacitors and micro-supercapacitors with superior volumetric capacitance due to the synergetic effect of the ultrathin pseudocapacitive thiophene nanosheets and the capacitive electrochemically exfoliated graphene.