Disclosed is a method of recovering 1,3-butadiene from a C4 stream containing butane, isobutane, 2-butene, 1-butene, isobutene, butadiene and acetylene. The process of recovering highly pure 1,3-butadiene includes acetylene conversion for selectively converting acetylene through liquid-phase hydrogenation, so that the acetylene content is decreased to 70 wt ppm or less, and 1,3-butadiene extraction using an extractive distillation column, a pre-separator, a solvent stripping column, a solvent recovery column, and a purification column. Through the acetylene conversion, the concentration of vinylacetylene is decreased to 70 wt ppm or less, after which 1,3-butadiene is recovered using only one extractive distillation column, thereby considerably decreasing the degree of utility and the loss of streams in the course of extraction. The number of units necessary for the process is decreased, thus remarkably reducing the time during which impurities can accumulate in a processing unit.