Abstract The upgrading of oleyl alcohol synthesis via methyl oleate reduction using NaBH 4 without H 2 supply was investigated. It was possible to synthesize selectively oleyl alcohol with high yields. Non‐catalytic and catalytic experiments were developed trying to improve the low final oleyl alcohol yield previously obtained. The effect of reaction temperature, methyl oleate/NaBH 4 molar ratio and properties of different catalysts on final oleyl alcohol yield were analyzed. Thus, alumina‐supported metal (M) catalysts (M = Fe, Ce, Mo) were synthesized by incipient wetness impregnation. The M/Al 2 O 3 catalysts were characterized in their chemical, textural, structural and acid–base properties using ICP, N 2 physisorption, XRD and temperature‐programmed desorption (TPD) of NH 3 and CO 2 . During non‐catalytic methyl oleate reduction, final methyl oleate conversion and oleyl alcohol yield of 94% were obtained using a methyl oleate/NaBH 4 molar ratio of 0.11 at 333 K. Catalytic activity of M/Al 2 O 3 solids increases as acid site number and ionic potential of M cations increase. In addition, the reaction mechanism for fatty acid methyl ester reduction was investigated from a theoretical approach using Density Functional Theory method at B3LYP/6‐31++G(d,p) computational level. Results obtained during theoretical calculations confirmed that the formation of reducing alcoxyborohydride species is energetically favored and allowed to understand the events at microscopic level involved in the reaction mechanism.