White matter (WM) alteration is considered to be a vital neurological mechanism of obsessive-compulsive disorder (OCD). However, little is known regarding the changes in topological organization of WM structural network in OCD. We acquired diffusion tensor imaging (DTI) datasets from 28 drug-naive OCD patients and 28 well-matched healthy controls (HC). A deterministic fiber tracking approach was used to construct the whole-brain structural connectome. Group differences in global and nodal topological properties as well as rich-club organizations were compared by using graph theory analysis. The relationship between the altered network metrics and the Yale-Brown Obsessive-Compulsive Scale (Y-BOCS) was calculated. Compared with controls, OCD patients exhibited a significantly decreased small-worldness (sigma), normalized clustering coefficient (gamma) and shortest path length (L-p), as well as an increased global efficiency (E-glob). The nodal efficiency (E-nodal) was found to be reduced in the left middle frontal gyrus, and increased in the right parahippocampal gyrus and bilateral putamen in OCD patients. Besides, OCD patients showed increased rich-club, feeder and local connection strength, and the connection strength of the rich-club was positively correlated with the total Y-BOCS score. Our findings emphasized a central role for the complicatedly changed topological architecture of brain structural networks in the pathological mechanism underlying OCD.