Oxocarbons, known for over two centuries, have recently revealed a long-awaited facet: two-dimensional crystalline structures. Employing an intelligent global optimization algorithm (IGOA) alongside density-functional calculations, we unearthed a quasi-flat oxocarbon (C6O6), featuring an oxygen-decorated hole, and a novel 3D-borocarbon. Comparative analyses with recently synthesized isostructures, such as 2D-porous carbon nitride (C6N6) and 2D-porous boroxine (B6O6), highlight the unique attributes of these compounds. All structures share a common stoichiometry of X6Y6 (which we call COF-66), where X = B, C, and Y = B, N, O (with X ≠ Y), exhibiting a 2D-crystalline structure, except for borocarbon C6B6, which forms a 3D crystal. In our comprehensive study, we conducted a detailed exploration of the electronic structure of X6Y6 compounds, scrutinizing their thermodynamic properties and systematically evaluating phonon stability criteria. With expansive surface areas, diverse pore sizes, biocompatibility, π-conjugation, and distinctive photoelectric properties, these structures, belonging to the covalent organic framework (COF) family, present enticing prospects for fundamental research and hold potential for biosensing applications.