Bottom-up process design is performed for a new antimony white fuming approach from antimony-rich lead refining residues. Thermochemical modelling is used to evaluate process boundaries regarding temperature and slag composition allowing the fuming of qualified antimony white from mentioned residues. Two methods are evaluated in laboratory scale to test possibilities of preconditioning for the fuming process. The first one is based on a more selective oxidation during lead softening; the second one on carbothermic reduction of the slag. Antimony enrichment is successfully proven under laboratory scale conditions.