A general and versatile synthetic strategy for producing practical quantities of a wide range of phenyl-group-terminated hetero- and homotelechelic semicrystalline polyethenes and amorphous atactic and semicrystalline isotactic poly(α-olefins) is reported. The phenyl groups serve as synthons for functionalities of additional classes of telechelic polyolefins that can be "unmasked" through simple high yielding postpolymerization reactions. A demonstration of the value of these materials as building blocks for structural classes of polyolefin-based synthetic polymers was provided by syntheses of well-defined polyolefin-polyester di- and triblock copolymers that were shown to adopt microphase-segregated nanostructured mesophases in the condensed phase.