The characterisation of a new system based on cashew-nut tree gum, a branched acidic heteropolysaccharide found in Brazil, and poly(ethylene glycol) (PEG) was studied. Phase diagrams are provided for the PEG-cashew-nut tree gum system. The influence of PEG molecular mass, tie-line length and pH on bovine serum albumin (BSA) partition was investigated. Protein partition coefficient was little influenced by changing PEG molecular mass. Increasing the tie-line length decreased the partition. Increasing the pH also raised the BSA partition coefficient. It is shown that systems formed by PEG and cashew-nut tree gum may be considered as an interesting alternative for use in protein purification.