Can the critical coalescence concentration (CCC) of the flotation frothers be predictable? What is the relation between their molecular structure and their CCC values? A literature survey found specific correlations between the hydrophilic-lipophilic balances (HLB) and HLB/Mw (where Mw stands for the molecular mass) of homologue series of frothers and their CCC values, but the results are invalid when the molecule's functional groups change. For this reason, 37 frothers with known values of CCC were analyzed. The CCC values of seven frothers were determined, and the rest were taken from the literature. The frothers were subdivided in homologue series with an increasing number of the carbon atoms with an account for the type and the location of the functional group, thus deriving three types of correlations lnCCC =f(HLB) applicable for: (i) alcohols; (ii) propylene glycols alkyl ethers and propylene glycols; (iii) ethylene glycols alkyl ethers. The average accuracy of these correlations between CCC and HLB is 93%.