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In this work, a psychophysical experiment is implemented to assess the white sensation of light-emitting diode (LED) lighting in illuminant mode via a categorical judgment method by a panel of 10 observers. The visual data indicates that the higher values of white sensation estimations locate near the Planckian locus within a correlated color temperature (CCT) range of 5000–9000 K. A model of white sensation for LED lighting in illuminant mode is proposed, from which the predicted maximal white sensation locates near the Planckian locus with a CCT of 6622 K, and the 95% white sensation covers a narrow two-dimensional region.