摘要： Preparation of large single crystals for linear polymers that are amenable to X-ray analysis is very challenging in polymer science. Herein, we employed a coordination driven self-assembly strategy to secure appropriate head-to-tail alignment of anthracene moieties, and for the first time obtained large-sized Pt-based linear polymer crystals through a [4+4] cycloaddition of anthracene in a single-crystal fashion. Using X-ray diffraction analysis to precisely determine polymer crystal structure, we revealed that both the polymerisation and depolymerisation steps proceed via a stable intermediate. Taking advantage of the temperature-dependent slow depolymerization, the afforded Pt-based linear polymer showed potential as a sustained release anticancer drug platform. Furthermore, utilizing the reversible contraction effect of unit-cell volume upon irradiation or heating, the stimuli-responsive crystals were hybridized with polyvinylidene fluoride to obtain a ‘smart material’ with outstanding photoactuator performance. This work not only provides a new approach to prepare metal-containing linear polymer crystals, but also broadens their potential applications towards drug controlled-release and actuator functions.