The invention relates to a novel titanium system heterogeneous catalyst composition and a preparation method thereof as well as application of the catalyst composition in the aspect of polymerization of isoprene. The synthesis method of the catalyst is simple and is easy to control, thus the heterogeneous, high-activity and stable catalyst is obtained. The titanium system heterogeneous catalyst composition disclosed by the invention can be used for synthesizing polyisoprene with cis-form structure content of more than 99%, weight-average molecular weight adjustable in a range of 100-300 ten thousand and molecular weight distribution of 3.0-4.0; and the polymerization process is stable and easy to control, thus the preparation method disclosed by the invention is suitable for continuous process operation.