The amount of calcium bound to protein was measured in 30 patients with differing diseases and varying degrees of hypoalbuminaemia. Total serum calcium increased directly with both serum albumin and ultrafilterable calcium concentrations. The estimated amount of calcium bound per gram of albumin varied inversely with the albumin concentration, decreasing from 2.1 to 1.0 mg calcium/g albumin as albumin concentration increased from 1.7 to 3.1 g/dl. Circulating parathyroid hormone (PTH) concentrations varied inversely with measured ultrafilterable calcium concentrations. The frequency of raised PTH concentrations decreased as serum albumin increased. Use of a conventional correction factor for albumin binding (0.88 mg calcium bound per gram of albumin) to calculate corrected total calcium led to major errors in estimating ultrafilterable calcium in these patients. The PTH concentrations in turn correlated with the degree of deviation between estimated and measured ultrafilterable calcium concentrations. Ionised calcium was low in seven of ten additional hypoalbuminaemic patients studied whereas correction of total calcium for albumin indicated normocalcaemia in all. Thus correction of total calcium in patients with hypoalbuminaemia by formulae which use a fixed binding ration of calcium to albumin may give an erroneous impression of normocalcaemia. The increase in calcium binding ratio during hypoalbuminaemia needs to be considered during assessment of calcium status in these patients.