The thermodynamic properties of arsenic in metal, speiss, matte, slag and gas phases are first summarised in this paper. Arsenic associates with sulphide minerals and generally has compounds of high volatility, but it has a weak affinity for sulphur and a strong affinity for metals, especially copper and iron. In the initial stage of the oxidation of sulphide concentrates arsenic is volatilised easily prior to the oxidation of FeS, although it tends to be fixed in the condensed phase as FeAsO4 if the concentrate is over-oxidised. Thermodynamic simulation of oxidative copper smelting reveals the distribution of arsenic between matte, slag and gas, and the possibility of condensation of arsenic from the resulting waste gas is discussed. In reductive smelting more arsenic remains in the metal or matte, and is sometimes concentrated as a separate speiss phase. The phase relations and thermodynamic properties of speiss are also summarised briefly. Arsenic refining from smelted copper metal is shown, from an examination of the basic principles of arsenic removal into slags, to be difficult. Owing to its weak affinity for lead however, arsenic refining from lead bullion is seen to be much easier.