2-Butyl-1-octene was used as the raw material for synthesis of 2-butyl-1,2-octanediol by hydroxylation catalyzed by HCOOH and H2O2, and the effect of experimental conditions on the selectivity of each product was investigated. It is showed that the synthesized 2-butyl-1,2-octanediol and 2-butyl-1-octanol had the same branched structure, having the potential replacing 2-butyl-1-octanol to synthesize various branched compounds. The structure of products was characterized by FTIR and GCMS. It was determined that the products containes not only 2-butyl-1,2-octanediol, but also 2-butyl-1-epoxyoctane, 5-undecone, 2-butyl-2-octenol, 2-butyloctanal, 2-butyloctanoic acid, and other substances. By single factor experiments, the optimized reaction conditions were obtained as follows: n(H2O2)/n(2-butyl-1-octene)=1.5, n(HCOOH)/n(2-butyl-1-octene)=3.5, reaction temperature was 30 ℃, reaction time was 6 h, and the conversion of 2-butyl-1-octene and the selectivity of 2-butyl-1,2-octanediol reached respectively 99.2% and 72.8% under these conditions. The synthesis of 2-butyl-1,2-octanediol makes up for the deficiency of the Guerbert reaction to synthesize 2-butyl-1-octanol and opens up a new way to synthesize high value-added fine chemicals by coal resource utilization.