NiFe-layered double hydroxide (NiFe-LDH) and La-, Mo- or W-doped NiFe-LDH microparticles (NiFeX-LDH, X = La, Mo, W) were synthesized via the co-precipitation method. Their adsorption characteristics were evaluated by the removal of methyl orange (MO) and hexavalent chromium (Cr6+). The effects of the metal ion doping type, doping concentration (0-3at%), pH and temperature on the MO adsorption properties were systematically studied. The results show that W-doped NiFe-LDH exhibits superior MO removal capacity compared to undoped or La- or Mo-doped NiFe-LDH at the same 1at% doping level, which is attributed to the increased layer charge density and strong affinity for the pi-electron systems of MO molecules. The NiFeW-LDH-1at% sample demonstrated the best MO adsorption performance within the W-doping range of 0-3at%, achieving a superior adsorption capability of 666.67 mg/g with a significantly shorter equilibrium time (10-120 min) compared to the similar LDH. NiFeW-LDH-1at% showed promising reusability, with its adsorption efficiency remaining 78.3% of its initial level after five adsorption-desorption cycles. The MO uptake onto NiFeX-LDH was attributed to the combined effect of anion exchange and the attraction of layer charge. In addition, the adsorption of NiFeW-LDH-1at% matched well with the Langmuir isotherm model and pseudo-second-order kinetic model, indicating a monolayer and chemical adsorption. Furthermore, NiFeW-LDH-1at% effectively adsorbed of Cr2O72- in the aqueous solution, revealing that W doping significantly enhances Cr(VI) removal performance. The maximum theoretical adsorption capacity onto NiFeW-LDH-1at% reached 63.25 mg/g, which was notably higher than that of the pristine NiFe-LDH adsorbent (53.56 mg/g). Overall, the W-doped NiFe-LDH material, as a low-cost and highly efficient adsorbent, shows great potential for wastewater treatment application.