Antibiotic contamination in aquatic ecosystems drives the dissemination of antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs). While heterogeneous photocatalysis using metal-free porous organic polymers (POPs) and covalent organic frameworks (COFs) offers a sustainable remediation strategy, current literature predominantly focuses on parent pollutant disappearance rather than fundamental degradation bottlenecks. This review critically addresses this gap by evaluating the inherent molecular trade-offs governing COF/POP design, the mechanistic pathways of real-water matrix interference, and the ecotoxicity of transformation products. Furthermore, we provide a critical Life Cycle Assessment (LCA) and Techno-Economic Analysis (TEA) perspective on synthesis versus performance, concluding with a standardized reporting checklist to guide future research toward practical, pilot-scale implementation.