Gas chromatograph (GC) and gel permeation chromatography (GPC) were used to investigate the activity sites of lignin, which influence the emulsifiability of emulsifier and mixing performance of cold-recycling asphalt mixture obviously, in this paper. It was found that the emulsifier A prepared by lignin A showed the highest activity in emulsifiability and mixing performance, which was due to its 9.48 activity sites on average. Moreover, emulsifier B synthesized by lignin B exhibited a lower activity on emulsifiability and mixing performance than that of lignin A, which was because lignin B had 7.68 activity sites. However, the mixing performance of emulsifier C could not satisfy the technical specifications for highway asphalt pavement recycling, which was attributed to its 4.42 activity sites only. The synthetic route of this emulsifier was simple and its performances used in cold-recycling were excellent; as such, this kind of emulsifier could have a promising application in the future.