Simultaneous removal of multi-component pollutants from atmosphere is crucial for personal protection. Herein, porous carbon spheres (PCSs) with 1.2mm diameter were prepared through the phase inversion route followed by carbonization using g-C3N4 and PVDF as precursors. The structure and chemical property of PCSs can be tailored via controlling the content of g-C3N4 due to its dual-function of template and nitrogen source. The resultant PCSs possess high surface areas, rich nitrogen content and favorable micro/meso/macro hierarchical porous structure, which are highly desired for simultaneous removal of benzene and H2S. The dynamic adsorption behaviors for benzene and H2S were investigated to examine the protective performance. Owing to the abundant porous structure and chemical polarity, PCSs extend the protective performance for H2S under retention of adsorption performance for benzene. The promotion on adsorption performance for H2S from mixture could be attributed to the change of electron distribution on nitrogen atom caused by the adsorbed benzene. The adsorption kinetic confirmed the enhancement on mass transfer ascribed to meso/ macro hierarchical porous structure. These results revel that PCSs would be a promising adsorbent in personal protective equipment for VOCs and TICs.