Several complexes containing the Ru-H bond were synthesized according to previous reports: RuH(NO)(PPh 3 ) 3 (I) (1), RuHCl(PPh 3 ) 3 (s)(II) (2), RuHCl(CO)(PPh 3 ) 3 (II) (3), RuH(CH 3 COO)(PPh 3 ) 3 (II) (4) and RuH 2 (CO)(PPh 3 ) 3 (II) (5), and characterized by 1 H NMR and IR spectra; the complex of RuHCl(PPh 3 ) 3 (s) was screened for further investigation on the basis of activity and life-operating on isomerization of 1-hexene and 1-octadecene in temperature; the influence of temperature, reaction time and catalyst concentration on 1-hexene isomerization by RuHCl(PPh 3 ) 3 (s) was carefully studied: 1-hexene was converted into other two isomers of 19.39% 2-hexene and 78.16% 3-hexene on the condition of catalyst 2 ร 10 -5 mol (in 1 ml toluene), temperature 120 โข C, time 30 min, 1-hexene 4 ml; while the performance on 1-octadecene isomerization by RuHCl(PPh 3 ) 3 (s) presented high activity, thermal stability and the solvent-free system: at 180 โข C the equilibrium conversion of 1-octadecene reached above 94.6% with the condition of the 1:200 (mol) ratio of catalyst to substrate; and the distinct differences were presented on the isomerization by RuHCl(PPh 3 ) 3 (s) for 1-hexene and 1-octadecene in reaction temperature, solvent, intermediate. The evidence on isomerization of 1-hexene and 1-octadcene by RuHCl(PPh 3 ) 3 (s) was provided to recognize the specifically isomerization process: the catalytic property was closely relation with coordination circumference of the centre metal, ligand property and substrate structure, and the mechanism was carefully studied on 2 as well.