Unraveling the nature of complex condensed matter systems is of paramount importance in a variety of fields such as pharmacology and materials science. Here we report the synthesis, by the dynamic covalent chemistry (DCC), of a robust, continuous, and low-defect glassy covalent organic network (GCON). The direct imaging of the molecular structure clearly shows the amorphous nature of GCONs, which consists with the competing (nano) crystallite model, not Zachariasen continuous random networks (Z-CRN). Remarkably, the microscopic friction properties were measured on GCONs by atomic force microscopy (AFM), and the GCONs showed lower friction force in comparison with crystalline covalent organic frameworks (COFs).