The results of this study are the first to show that high-1,4 linear α,ω-dihydroxypolydienes can be synthesized with (a) predictable molecular weights, (b) narrow molecular weight distributions, and (c) high functionalities. Using the functionalized polyisoprenes prepared in this work, a series of networks was prepared with a purified triisocyanate as the chain linking agent. The soluble fraction in these networks ranged from 4.6 to 1.6 per cent. The characteristics and physical properties of these networks will be the subject of a forthcoming publication.