The direct growth of two-dimensional (2D) materials on the surface of insulating substrate holds significant promise for the construction of electronic and optoelectronic devices, facilitating the adaption to semiconductor manufacturing lines, but remains challenging. Herein, we present a facile and effective method for the direct synthesis of novel 2D SiO2 domains and as-orientated graphene arrays with assist of copper vapor by chemical vapor deposition (CVD). The morphology engineering of SiO2 domains has been realized by modulating the growth temperature and time with high reproducibility and outstanding uniformity. Moreover, our method results in the formation of hexagonal graphene arrays featuring a highly aligned orientation on the as-grown SiO2 flakes. These spontaneously formed vertical heterostructures provide an opportunity to directly construct devices without chemical etching transfer. As a result, the field-effect transistor (FET) based on the spontaneously formed graphene/2D SiO2 heterostructure performed an ultrahigh charge mobility of 3,800 cm2 V-1 s-1. The controllable synthesis of a 2D SiO2 array and SiO2/graphene heterostructures opens up broad prospects for tailoring customized 2D materials, enabling a significant step towards realizing the full potential of 2D materials in electronic and optoelectronic device fabrication.