Forty-eight cultivars (44 landraces and 4 hybrids) of white yam (Dioscorea rotundata Poir.) selected as parents for a breeding program in Benin were evaluated for proximate, sugars and mineral composition using standard AOAC methods. The results revealed a great variation among cultivars for fat (2.4-18 mg/g), protein (0.40-19.31 mg/g), total sugars (28.60-498.97 mg/g), reducing sugars (50-156.27 mg/g), and starch (44.82-400.41 mg/g) content. Variations in mineral content (mg/100g) were also noted among cultivars for Calcium (12.20 to 560.80 mg), Magnesium, (1.65 to 1630.80 mg), Iron, (1.79 to 22.60 mg), Zinc (0.55 to 20.03 mg) and Phosphorus (13.08 to 152.48 mg). Fat content were positively correlated with starch and negatively correlated with protein content. UPGMA cluster analysis assembled cultivars into 03 groups (G1, G2, G3). Cultivars of G1 and G3 are characterized with higher levels of sugars, lipids, proteins, starch, dry matter and significant mineral content. They appear to be more promising for involvement in breeding programs.