In this paper, hydrophobic carbon nanotube (CNT) arrays, ropes, and agglomerates were synthesized through self-organization on quartz substrates with different micro-structures under the same growth condition. On a flat substrate, a uniform woven structure was formed which resulted in a synchronous growth into an array. When the substrate with 10 µm round concaves distributed on the surface was adopted, the woven structure was sporadic and a CNT cluster was grown in the concave. With further growth, CNT ropes were self-organized. Subsequently, when the substrate consisting of irregular ∼100 nm gaps was used, the initial woven structure was high density, thus resulting in the formation of CNT agglomerates. Study results showed that CNT arrays grown on the flat substrate were of the highest purity and had a contact angle of 153.8 ± 0.9°. Thus, the self-organization behavior among CNTs was in situ modulated by different substrate morphology without further treatments. This provides us with an additional understanding of the self-organization of CNTs during growth, as well as strategies for the controllable synthesis of CNTs with fixed properties.