Channel-aligned regulation of photoelectrode within the bulk structure to generate eminent light absorbance and high-level pollutant adsorption is pivotal but challenging for realizing high-performance photofuel cell (PFC) system. Herein, we demonstrated an effective and scalable expansion-flow-modulated direct ink writing (DIW) 3D printing strategy for controllably constructing microlattice photoelectrode, with multiscale well-interconnected oriented channels built by layer-by-layer highly-regular assembly of filaments and vertical alignment of graphene nanosheets within filaments as well as uniform coupling of abundant photoactive nanoparticles to highly ordered channel walls. The unique architectural features enabled high-speed and effective diffusion/trapping of wastewater pollutants throughout the entire photoelectrode, and meanwhile facilitated ready spreading of incident light into the photoelectrode interior to yield high light absorption. As a result, an integrated 3D-printed vertically-aligned PFC (3DP VAPFC) assembled with as-fabricated photoelectrode exhibited its powerful capability for efficiently converting wastewater pollutants into electric energy under sunlight, with remarkable cycling stability and maximum power density of 0.11 mW cm−2. This work opens a promising route for architecting advanced photoelectrode toward PFC devices with highly efficient degradation and electricity generation of pollutants.