The invention discloses a preparation process of low-iron 4N gallium. The preparation process comprises the following steps: step 1, adding a gallium-containing solution stock solution to an electrolytic cell; step 2, electrolyzing the gallium-containing solution stock solution for 5 hours at the current density of 0.137A/cm<2>, and separating high-iron metal gallium out of the electrolytic cell;and taking out the high-iron metal gallium in the electrolytic cell, and using the residual solution in the electrolytic cell as a low-iron gallium preparation solution; step 3, electrolyzing the low-iron gallium preparation solution prepared in the step 2 at the current density of 0.119A/cm<2>, controlling the electrolysis time of the low-iron gallium preparation solution within 20 hours, separating out the low-iron metal gallium from the electrolytic cell, and taking out the low-iron metal gallium for later use; and step 4, feeding the low-iron metal gallium prepared in the step 3 into a crystallization tank of which the temperature is lower than the melting point of gallium, and conducting crystallizing to prepare the low-iron crystal gallium. By means of the preparation process, the content of Fe in the 4N gallium product can be reduced, it is guaranteed that the 4N gallium product can meet the quality standard for preparing high-purity gallium, and the yield of high-purity galliumis increased.