New main-chain type poly(5,8-dialkoxyanthraquinone-1,4-diyl)s have been prepared by using a Ni(0) complex. They take an ordered structure assisted by side-chain crystallinity. The ordered structure has been elucidated by X-ray diffraction pattern. Their d spaces and the relationship between the d space and the number of carbon atoms in the alkoxyl side chain indicate that these polymers take an end-to-end packing mode and their main chain has an s-trans conformation. These polymers exhibit liquid crystalline behaviour at a wide range of temperature.