Potato starch was blended with defatted milk in proportions providing a 4:1, 3:1, 2:1, 1:1, 1,:2, 1:3, and 1:4 starch/casein ratio. Precipitation was achieved by addition of either hydrochloric acid or leaven. Composition of precipitated products was determined based on elemental analysis for nitrogen. Generally, differences between attempted and achieved casein-to-starch proportions did not exceed 10%. Products coprecipitated with hydrochloric acid were slightly richer in casein than products obtained with leaven. Aqueous solubility, water binding capacity, IR spectra, and thermal analysis (thermogravimetry, TG, and differential thermogravimetry, DTG) were recorded for the precipitates. Analyses revealed that the precipitates were not simple physical mixtures of the components. Partial insolubility in 7 M aqueous urea showed that casein and potato starch are chemically bound. Comparison of the spectra and thermograms suggested that complexes of the 1:1 composition were formed constituting a nucleus of the aggregates carrying excessive amounts of either starch or casein.