Layered double hydroxides (LDHs) are currently attracting intense research interests as pollutant adsorbent due to its low cost, non-toxicity, structure amenability and anion exchange capability. Herein, 3-dimensional (3D) flower-like Ni/Al LDH were prepared to decorate H3PO4 activated biomass-derived porous carbons (PAB) via a facile and green hydrothermal method. The as-synthesized nanocomposites (Ni/Al@PAB) displayed favorable removal performance towards both Cr(VI) and methyl orange (MO) from aqueous solution due to the inherited excellent Cr(VI) removal ability from PAB and MO removal ability from Ni/Al LDH. In single-component removal system, the maximum adsorption capacity of 271.5 and 412.8 mg/g for Cr(VI) and MO were achieved on Ni/Al@PAB, respectively. Remarkably, the removal capacity of Cr(VI) and MO both increased in the Cr(VI)-MO binary system due to the synergistic effect including, (i) additional adsorption sites of N-containing groups from MO, (ii) electrostatic interactions by the reduced Cr(III), and (iii) mutual thermal compensation in the binary system. This work paved the way for designing novel LDHs-decorated porous carbon adsorbents and revealed that the acicular Ni/Al LDH decorated PAB could be applied as efficient and simultaneous adsorbent for coexisting toxic pollutants situations.