So far, achieving high apparent quantum yield (AQY) in polymeric photocatalysts at wavelengths up to 500 nm has never been achieved. Covalent organic polymers (COPs) have the advantage of high structure function tunability. However, despite decades of development, COPs still lag in achieving high AQY value, highlighting the need for an optimal COP structural design for efficient photocatalysis. Herein, we present a green synthetic approach to synthesize five hydrophilic and non-conjugated linkage with D-π-A system benzoin-based COPs by self-condensation of multiformly monomers. Charge kinetic carrier and femtosecond transient absorption (fs-TAS) demonstrate the efficient charge transport of benzoin-based COPs. Among the synthesized photocatalysts, B-PyTT-COP (D-π-A) outperforms the COP family, with an excellent HER of 233.81 µmol h⁻¹ (77935 µmol g⁻¹h⁻¹) using Platinum as co-catalyst. Remarkedly, B-PyTT-COP has achieved an exceptional ability to generate a high AQY value at 500 nm (65.35 %), surpassing all other materials examined thus far.