• NiMo-MMO catalyst derived from LDHs achieves ~95% pyrene conversion and 90.12% selectivity for deep hydrogenation products.
• Structural topological transformation from LDHs precursors enhances metal dispersion and catalyst stability.
• Synergistic effects between Ni and Mo, along with metal-support interactions, are crucial for deep hydrogenation activity.
• The catalyst provides a theoretical basis for designing non-noble metal catalysts for PAHs hydrogenation.