The present invention relates to a purification apparatus capable of selectively performing bio-catalytic combustion on VOC waste gas, and a use method thereof. The purification apparatus comprises a filtration screen, a biological trickling filtration tower, a dehumidifier, a first active carbon adsorption device, a second active carbon adsorption device, a catalytic combustion device, a heat exchanger, and an exhaust fan. The use method comprises two treatment processes, wherein the first treatment process comprises that filtration is performed with the filtration screen, adsorption is performed with active carbon, and waste gas is discharged, and the second treatment process comprises that filtration is performed with the filtration screen, degradation is performed with the biological trickling filtration tower, drying is performed with the dehumidifier, one part of waste gas is conveyed to the active carbon adsorption device so as to be adsorbed, the other part is heated by the heat exchanger, one part of the heated waste gas is conveyed to the active carbon adsorption device so as to be adsorbed, the desorbed waste gas is conveyed into the catalytic combustion device so as to be combusted, and the other part of the heated waste gas passes through the biological trickling filtration tower so as to heat the circulation liquid. With the purification apparatus of the present invention, the treatment processes can be flexibly switched according to the amount of the waste gas or the concentration of the organic matters so as to ensure the continuity of the waste gas treatment and achieve the resource reuse of the organic matters in the waste gas.