A novel perylene tetracarboxylic acid bisimide (PTCBI) in-chain polyethylene (PE) was first prepared via acyclic diene metathesis (ADMET) polymerization of PTCBI-functionalized α,ω-diene monomer. The polymers could spontaneously self-assemble into hollow cylindrical structures in which the π-π interaction between adjacent PTCBI moieties was enhanced and the electron mobility was possibly promoted. The hydrogenation of as-obtained polymer was readily accomplished, affording the desired precision PTCBI in-chain PE with a saturated backbone, which showed high glass transition temperature (Tg = 63 °C), relatively wide range of light absorption (λ = 200−575 nm), and higher LUMO level (−3.62 eV). It can therefore serve as a superior model for facile construction of functional polyolefin and soluble PTCBI polymer with ordered architecture.