Improving sweet–waxy corn hybrids enriched in carotenoids via a hybrid breeding approach may provide an alternative cash crop for growers and provide health benefits for consumers. This study estimates the combining ability and heterosis of sweet–waxy corn hybrids for yield-related traits and carotenoids. Eight super sweet corn and three waxy corn lines were crossed to generate 24 F1 hybrids according to the North Carolina Design II scheme, and these hybrids were evaluated across two seasons of 2021/22. The results showed that both additive and non-additive genetic effects were involved in expressing the traits, but the additive genetic effect was more predominant. Most observed traits exhibited moderate to high narrow-sense heritability. Three parental lines, namely the ILS2 and ILS7 females and the ILW1 male, showed the highest positive GCA effects on yield-related traits, making them desirable for developing high-yielding hybrids. Meanwhile, five parental lines, namely the ILS3, ILS5, and ILS7 females and the ILW1 and ILW2 males, were favorable general combiners for high carotenoids. A tested hybrid, ILS2 × ILW1, was a candidate biofortified sweet–waxy corn hybrid possessing high yields and carotenoids. Heterosis and per se performance were more positively correlated with GCAsum than SCA, indicating that GCAsum can predict heterosis for improving biofortified sweet–waxy corn hybrid enriched in carotenoids. The breeding strategies of biofortified sweet–waxy corn hybrids with high yield and carotenoid content are discussed.