New adsorption gels were prepared by chemically immobilizing functional groups of ethylenediamine, diethylamine and/or triethylamine on orange waste, named OW-en, OW-DEA, and OW-TEA, respectively. By comparing with the adsorption of other coexisting metals, such as Re(VII), Pb(II), Fe(III), Zn(II), Mn(VII), Ca(II), and Cu(II), the novel gels exhibited selectivity only for Mo(VI) and the adsorption behavior obeys the Langmuir model. The maximum adsorption capacity for molybdenum was in the order, OW-en (2.17 mol/kg) > OW-TEA (1.26 mol/kg) > OW-DEA (0.88 mol/kg). A kinetic study for the adsorption of molybdenum at various temperatures confirmed that the endothermic adsorption process followed pseudo-second order kinetics. In addition, its excellent adsorption characteristics for Mo(VI) were confirmed by the adsorption and elution tests using a column packed with the OW-en gel, especially by separation of Mo(VI) from Mo-Re containing industrial effluent.