The Phase Inversion Temperature of a reference CloEdn-Octane/Water system exhibits a quasi-linear variation versus the mole fraction of a second surfactant 52 added in the mixture. This variation was recently proposed as a classification tool to quantify the Hydrophilic Lipophilic Balance (HLB) of commercial surfactants. The feasibility of the so-called PIT-slope method for a wide range of well-defined non-ionic and ionic surfactants is investigated. The comparison of various surfactants having the same dodecyl chain tail allows to rank the polar head hydrophilicity as: SO3Na SO4Na >= NM(e)3Br > E2SO3Na CO2Na EISO3Na >= PhSO3Na approximate to Isosorbide(exo) SO4Na >> Isosorbide(endo). Glucosyl > E-5 >= Diglyceryl >= E-4 > E-3 > E-2 Isosorbide(exo) > Glycelyl> Isosorbide.n. The influence on the surfactant HLB of other structural parameters, i.e. hydrophobic chain length, unsaturation, replacement of Na by counterion, and isomerism is also investigated. Finally, the method is successfully used to predict the optimal formulation of a new bio-based surfactant, 1-0-dodecyldiglycerol, when performing an oil scan at 25 degrees C. (C) 2015 Elsevier Inc. All rights reserved.