The invention belongs to the technical field of polymer synthesis, and specifically discloses a preparation method of a butadiene/1,3-pentadiene random copolymer. According to the preparation method, in the absence of water and oxygen, an organic alkali metal initiator is adopted, a randomization additive is added, butadiene and 1,3-pentadiene carry out copolymerization reactions to obtain the butadiene/1,3-pentadiene random copolymer, the mass ratio of butadiene to 1,3-pentadiene is 1:9-6:4, the reaction temperature is 0 to 100 DEG C, and the reaction time is 1 to 24 hours. The results show that the prepared butadiene/1,3-pentadiene random copolymer has the advantages of controllable molecular weight, adjustable molecular weight distribution, high randomization degree, controllable microscopic polymer structure, low glass-transition temperature (Tg=-70 to -40 DEG C), quick reaction rate, and high monomer conversion rate (100%).