This work pioneers a transformative template-concurrent synthesis paradigm that addresses intrinsic COF limitations by modulating reaction kinetics and thermodynamics. The 3DOM structure expedites mass transport and hole diffusion, while the S-scheme heterojunction directs charge separation and reduces activation barriers. Beyond enabling record-breaking dual-functional photocatalysis, the strategy provides fundamental design principles for porous materials, with broad implications for energy conversion (H₂ production), sustainable chemical synthesis (imines), and environmental remediation.