This molecular dynamics (MD) simulation carries a detailed analysis of a pressure-induced structural transition supercooled liquid and amorphous silicene (a-silicene). Low-density models of supercooled liquid and a-silicene containing 10 000 atoms are obtained by rapid cooling processes from the melts. Then, an a-silicene model at T = 1000 K, a supercooled liquid model at T = 1500 K and a liquid silicon model at T = 2000 K have been isothermally compressed step by step up to a high density in order to observe the pressure-induced structural changes. Specifically ‘Cairo tiling’ pentagonal and square lattices of silicene are discovered in our calculations. Structural properties of those penta-silicene and tetra-silicene models have been carefully analyzed through the radial distribution functions, interatomic distances, bond-angle distributions under high-pressure condition. The dependence of pressure on formation behaviors is calculated via pressure–volume and energy–density relationships. The first order transition from low-density supercooled liquid/amorphous silicene to highdensity penta-silicene and continuous transition from low-density liquid to high-density tetrasilicene are discussed. Atomic mechanism and sp3/sp2 hybridization evolution are inspected whereas the role of low-membered ring defects/boundary promises remarkable application and advanced research in future.