Charge generation and separation have been regarded as the main constraints limiting the photocatalytic activity of polymeric photocatalysts. Herein , two new linear polyarylether-based polymers (PAE-CPs) with different linking patterns between their donor and acceptor motifs have been tailor-made to investigate the influences of different linking patterns on the charge generation and separation process. Theoretical and experimental results unravel that compared to the traditional single-stranded linking pattern, the double-stranded linking pattern theoretically helps to strengthen donor-acceptor interaction of PAE-CPs and generate the coplanar structure to facilitate the charge generation and separation, as well as red-shift light absorption. With these prominent advantages, the PAE-D with double-stranded linking pattern assumes a greatly enhanced photocatalytic activity than the single-stranded linking pattern analogue (PAE-S), facilitating the rational design and modification of organic semiconductors for charge-induced reactions.