AbstractEthanol Guerbet condensation is an environmentally friendly process for preparing biofuel such as n‐butanol and alcohols with more than 4 carbon atoms. In this work, a multifunctional catalyst Ni/TiO2 was prepared by an excess impregnation method and its catalytic performance for ethanol Guerbet condensation was evaluated. The selectivity of C4‐C8 alcohols reached up to almost 70% (41.4% of n‐butanol) at nearly half conversion of ethanol at 210 °C and 10 h. Based on GC‐MS analysis results, the products in ethanol Guerbet condensation were identified and a reaction network was established. The presence of acetaldehyde and 2‐crotonaldehyde in the reaction products verified that Ni/TiO2‐catalyzed ethanol condensation followed the traditional dehydrogenation‐condensation‐hydrogenation reaction mechanism.