Hierarchical porous carbons equipped with heteroatoms and diffusion pores have a wide application prospect in adsorption. Herein, we report N-autodoped porous carbons (PTPACs), which were derived from rigid N-rich conjugated microporous poly(aniline)s (CMPAs) and show their all-around applicability in heavy metal adsorption. Their molecular structure could be delicately tuned from 3D organic networks to graphitic carbons through simply adjusting the pyrolysis temperature, affording unique hybrid features of hierarchical micro-meso-macroporosity and amount-tunable nitrogen defects, as validated by the enhanced CO2 adsorption capacities reaching 5.0 mmol g-1, a 230% increase compared to the precursor (2.15 mmol g-1). They therefore show promising a Langmuir adsorption capacity of 434.8 mg g-1 toward mercury ions, which could be rapidly achieved within a short 20 min. Based on the comprehensive experimental, characterization, and DFT calculation studies, we rationally reveal these impressive adsorptions arise from the hybrid function of chemisorption contributed by populated nitrogen defects and physical adsorption achieved by synergistic functions in the diffusion and storage pores. Outcomes mark the high merits of PTPACs in addressing recent global challenges in environmental engineering.