Sustainable and comprehensive recycling of valuable elements from waste SmCo magnets is crucial. In this work, an environmentally friendly process based on low viscosity and easy preparation of hydrophobic deep eutectic solvent (HDES) for comprehensive recovery of Fe(III), Co(II), Cu(II) and Sm(III) from waste SmCo magnets has been developed. The HDESs based on dodecanol (Dodec) and tri-n-octylphosphine oxide (TOPO) were prepared, characterized and first used to selectively extract Fe(III) and Sm(III) from the SmCo magnets leachate. And then the Cu(II) and Co(II) in the raffinate were selectively separated using decanoic acid (DA):lauric acid (LA) (2:1) based HDES. The batch counter current extraction experiment was carried out under optimal conditions. After two-stage extraction by using Dodec:TOPO (2:1) based HDES, over 99% of the Fe(III) and Sm(III) were extracted into the organic phase. Subsequently, the raffinate containing Co(II) and Cu(II) was subjected to single-stage extraction and three-stage scrubbing using DA:LA (2:1) based HDES. Fe(III) and Sm(III) loaded in the Dodec:TOPO (2:1) based HDES phase could be stripped by using 1.5 mol/L H2C2O4. The obtained Fe2(C2O4)3 solution and Sm2(C2O4)3 precipitate were separated by filtration. And the Cu(II) loaded in the DA:LA (2:1) based HDES phase was stripped by using 1 mol/L H2SO4. Finally, Fe(III), Co(II), Cu(II) and Sm(III) were completely separated, and the purity of each product can reach 98.50% or higher. The recovery rates of Fe(III), Co(II), Cu(II) and Sm(III) were 99%, 99%, 96.47% and 99%, respectively. The process has lower chemical consumption and no need to use volatile and toxic organic solvent, which is conducive to cleaner and safer production.