Covalent organic frameworks(COFs)are an emerging class of crystalline porous polymers with atomically precise orderings of organic components.The recent synthetic progress has shown that COFs are powerful platform for designing π-electronic porous materials,whereas two-dimensional polymer sheets are stacked in a superimposed way to generate periodic π-columnar arrays and one-dimensional open nanochannels.1 We have developed molecular design principle and synthetic methods for the construction of π-electronic porous COFs(Figure 1).2-21 In this talk,we will focus on our recent challenge for designing electron donor–acceptor COFs that enable the creation of segregated yet bicontinuous superheterojunction polymers,which provide a new molecular mechanism for optoelectronics and photovoltaics.