This study investigated the application of a magnetic organic phase containing hydrophobic superparamagnetic nanoparticles to accelerate phase disengagement in solvent extraction processes. For this purpose, stearate-modified magnetite nanoparticles were prepared, characterized, and dispersed in 20 vol.% D2EHPA extractant diluted in kerosene to obtain the intended organic phase. The magnetic solvent extraction process of nickel was conducted using the as-prepared magnetic organic phase containing varying concentrations of hydrophobic magnetite nanoparticles in a sulfate medium. The results implied significant decrements of up to four times in the aqueous/organic phase disengagement duration in an external magnetic field with 10 g.L−1 nanoparticles determined as the optimum concentration. Such magnetically accelerated separation was revealed to be the result of colliding and coalescing the size-heterogeneous magnetic organic droplets moving unevenly through the continuous aqueous solution in a separating system. It is also worth mentioning that applying magnetic solvent extraction did not affect the equilibrium extraction behavior of nickel by D2EHPA.