The present invention relates to a process for separating the isoprene, 1,3-pentadiene and dicyclopentadiene from a C5 cuts, comprising dimerization of the cyclopentadiene and selective catalytic hydrogenation. The second extractive rectification step can be omitted, because the alkynes are removed through selective catalytic hydrogenation prior to the extractive rectification. As a result, the solvent-recovering units can be simplified, and thus the process as a whole can be optimized. Correspondingly, the investment and energy consumption, the operation cost, and finally the production cost can be substantially reduced.