Five saturated alpha-branched fatty acids, also known as Guerbet acids, including alpha-propylhexyl acid (G (1) ), alpha-butylhexyl acid (G (2) ), alpha-propyloctyl acid (G (3) ), alpha-butyloctyl acid (G (4) ), and alpha-hexyloctyl acid (G (5) ), were synthesized in high yields by four-step reaction. Colorless, almost odorless, and oily products were obtained with high purity, whose structures were confirmed by GC, H-1/C-13 NMR, and ESI-MS characterization. G (1) , G (3) , and G (4) had pour points lower than -60 A degrees C, while G (2) and G (5) showed higher pour points (-42 A degrees C and 6 A degrees C, respectively) because of their molecular symmetry. Considering the low-temperature properties, G (1) , G (3) , G (4) , and even G (2) held great potential applications in the lubricant and oilfield.