d-Psicose/allulose is a rare sugar and it has high potential benefits for pharmaceutical and food industry. The existed analytical methods have its own limitations to quantify fructose and d-psicose mixtures. Hence there is a need for the development of an effective, efficient and sensitive analytical method for quantification of d-psicose in presence of other sugars. Quantification of sugars by capillary electrophoresis (CE) have been previously reported. However, the list does not include d-psicose. In this study, d-psicose is successfully quantified for the first time in the presence of d-fructose and glucose with a good resolution. Standard curves for all the sugars are established in a concentration range of 0.1 mM (0.0018% w/v) to 3.0 mM (0.0540% w/v) with a coefficient of determination of >0.99. The scope of this method can be extended to quantify d-psicose and their processed impurities in food products with minor modifications in sample preparation.