Surfactants are used in a vast array of products including pharmaceuticals, cosmetics and household formulations. From an industrial perspective, non-ionic surfactants are ideal for inclusion within such products as they are non-toxic, simple to formulate and economic to use. This study considers five non-ionic surfactants (Tween 20, Tween 80, Crodasol, Croduret and Etocas 35) to determine the critical micellar concentration (CMC) for each using isothermal titration calorimetry, thus avoiding issues regarding poor accuracy found with other techniques. Furthermore, this methodology has not previously been applied to this group of surfactants. For the most commonly used non-ionics (Tween 20 and Tween 80) a further study was undertaken to consider the influence of surfactant purity on the CMC determined, using standard grade (Tween 20 and 80), high purity (Tween 20 HP and Tween 80 HP) and Super Refined (SR PS20 and SR PS80). Results permitted calculation of the CMC for the surfactants whereupon the values were determined to range from 1.0 mM for Tween 20 HP to 2.9 mM for Tween 80 HP. Such information regarding the CMC event is useful from a formulation perspective as it can ensure that the most optimum concentration of surfactant is included within a formulation to maximize its efficacy.