The refractometer has been proposed as a rapid, inexpensive technique for determining sugar levels in fresh sweet corn (Zea mays). High performance liquid chromatography (HPLC) analysis of sugars in three phenotypes (su, se, and sh2) of sweet corn harvested at three maturities indicated that sucrose content was highly correlated with the total sugars (R = 0.95). Sucrose and total sugar concentration were significantly different among all phenotypes. Soluble solids concentration (SSC) was high in su and se compared to the lower SSC of sh2. Early, mature, and late harvested samples differed in sucrose and total sugar content. Sugar concentration varied within phenotypes at each maturity level. Sh2 indicated no difference in sucrose and total sugars at early and mature harvests, but increased at late harvest. In contrast, sucrose and total sugar content decreased between early and mature harvests, then increased to highest levels at late harvest in se and su phenotypes. Overall, phenotype SSC increased significantly from early to late harvests, probably due to increased water-soluble polysaccharides in the su and se cultivars. Unlike other crops, a negative relationship was found in sweet corn between SSC and sucrose or total sugars, with an overall correlation of –0.51. This relationship was most affected by maturity, especially mature and late harvested sweet corn. Among phenotypes, sucrose, total sugar, and SSC were poorly correlated. Our results indicate that a refractometer should not be used to estimate total sugars or sucrose of sweet corn.