Rhenium (Re) is an industrially important metal because of its use in catalysts and additives in alloys. Due to the rarity and maldistribution of Re, stabilization of its price and supply by recycling is quite important. Therefore, it is necessary to develop Re recovery methods from acid leach solutions of spent catalysts and alloys. In this study, we present a new Re recovery method using primary amines from Re-containing hydrochloric acid (HCl). Re was successfully recovered from HCl solutions as precipitates using 4-hexylaniline (HexAni). Separation of platinum (Pt) and Re was achieved using 2-ethylhexylamine and HexAni as precipitants, respectively. We also succeeded in the selective and quantitative precipitation of Re using HexAni from the HCl solution containing Re, aluminum, vanadium, cobalt, and nickel. Precipitation recovery method of Re using HexAni from HCl solutions is a promising candidate for Re separation and recycling.