Frothers are surfactants commonly used to reduce bubble size in mineral flotation. This paper describes a methodology to characterize frothers by relating impact on bubble size reduction represented by CCC (critical coalescence concentration) to frother structure represented by HLB (hydrophile-lipophile balance). Thirty-six surfactants were tested from three frother families: Aliphatic Alcohols, Polypropylene Glycol Alkyl Ethers and Polypropylene Glycols, covering a range in alkyl groups (represented by n, the number of carbon atoms) and number of Propylene Oxide groups (represented by m). The Sauter mean size (D 32 ) was derived from bubble size distribution measured in a 0.8 m 3 mechanical flotation cell. The D 32 vs. concentration data were fitted to a 3-parameter model to determine CCC95, the concentration giving 95% reduction in bubble size compared to water only. It was shown that each family exhibits a unique CCC95-HLB relationship dependent on n and m. Empirical models were developed to predict CCC95 either from HLB or directly from n and m. Commercial frothers of known family were shown to fit the relationships. Use of the model to predict D 32 is illustrated.