Ethanol is a considerable platform molecule in biomass conversion, which could be acquired in quantity through acetone-butanol-ethanol (ABE) fermentation. People have been working on the upgrading of ethanol to value added chemicals for decades. In the meantime, 1-butanol and a series of value added products have been selectively generated through C–C bond coupling. In this mini-review, we focus on the recent advances in selective C–C bond formation over balanced Lewis acid-base catalysts such as modified metal oxide, mixed metal oxide, hydroxyapatite and zeolite confined transition metal oxide catalysts. Among them, Pd-MgAlO x and Sr-based hydroxyapatite exhibit >70% 1-butanol selectivity, while Zn x Zr y O z and Ta-SiBEA zeolite achieve >80% of isobutene and butadiene selectivity respectively. The mechanism and reaction pathway of C–C bond formation in each reaction system are described in detail. The correlation between C–C bond coupling and the acidity/basicity of the Lewis acid-base pairs from the surface of the catalysts are also discussed.