The present invention is a process for producing high diblock content block copolymer compositions which comprises (a) anionically polymerizing at least one vinyl aromatic hydrocarbon and at least one conjugated diene to form a living block copolymer, (b) coupling the block copolymer with a coupling agent selected from the group consisting of esters of carboxylic acids and asymmetric silanes to create a coupled polymer, (c) combining the coupled polymer with other components to form an enduse composition, and (d) heating the composition at a temperature up to 130.degree. C. for a time sufficient to decouple the coupled copolymer such that the amount of uncoupled copolymer in the composition ranges from 10 to 100% by weight of the total amount of block copolymer.