A high-efficiency clean burning method of a macromolecular substance, wherein the macromolecular substance comprises biomass and solid organic waste; the method comprises the following steps: generating a first gaseous substance and a red-hot carbon residue layer from biomass carbon residue or charcoal or coke or a mixture thereof by anoxic combustion; leading the heat generated by anoxic combustion to the macromolecular substance, preheating and drying the macromolecular substance and carrying out pyrolysis gasification, so as to generate a second gaseous substance; taking red-hot carbon residue as a pyrolysis catalyst, leading the second gaseous substance to the red-hot carbon residue layer to carry out oxygen catalytic cracking, so as to generate a third gaseous substance; leading the third gaseous substance and the first gaseous substance to an oxygen-enriched combustion zone in a heat preservation manner to carry out oxygen-enriched combustion, so as to achieve substantial complete combustion of all gasification products, wherein a tar wastewater is not generated, and pollution of smoke tar is not generated. A device capable of achieving the method comprises four categories of a plurality of devices. Thus, zero emission of “dioxin” can be achieved when the device is applied to waste incineration disposal.