Hot ethanol–water solutions can be used to simultaneously fractionate and purify softwood Kraft lignin through the Aqueous Lignin Purification with Hot Agents (ALPHA) process, using the regions of liquid–liquid equilibrium (LLE) that form at selected temperatures and solvent‐to‐lignin feed (S/F) ratios. Lignin, ethanol, and water compositions are measured for the solvent‐rich (SR) and lignin‐rich (LR) liquid phases in mutual equilibrium, as well as the lignin and metals mass distributions between the two phases. As depicted in quasi‐ternary diagrams for clarity, both temperature and S/F ratio can be used to grow, merge, and even split the regions of LLE, giving significant control over both molecular weight (MW) and lignin purity. For example, a solvent comprising 45:55 EtOH/H2O at 75 °C and an S/F ratio of 6:1 enables recovery of an ultrapure (95 % of Na removed), higher MW (Mn=8400 Da) lignin fraction in the LR phase. On the other hand, 95:5 EtOH/H2O at 45 °C and S/F=3:1 enables recovery of an ultrapure, low MW (1500 Da) lignin in the SR phase.