Abstract Phosphorene is a recently discovered member of the two-dimensional (2D) monolayer materials, which has been reported to exhibit unique characteristics on mechanical and thermal properties. This study is the first time to show the exceptional thermal conductance between phosphorene and crystalline silicon substrate through classical molecular dynamics (MD) simulations. MD simulations revealed that under conventional conditions, the interfacial thermal resistance (R) between phosphorene and silicon is very low and independent on the thickness (h) of silicon substrate when h is larger than 3.12 nm. It was also found that R decreases remarkably with the increases in system temperature (Tie) and contact strength (χ). To further explicitly display the superiority of phosphorene on interfacial heat transfer, R of other two popular 2D monolayer materials, i.e., graphene and silicene, were calculated for comparison. The comparisons revealed that R of phosphorene shows two distinct advantages over graphene and silicene. On one hand, within the studied ranges of Tie and χ, R between phosphorene and silicon substrate is about quarter of that between graphene and silicon substrate, which proves that phosphorene is really a high-performance 2D monolayer material for interfacial heat transfer. On the other hand, with the increases in Tie and χ, R between phosphorene and silicon substrate decreases more sharply than that between silicene and silicon substrate, indicating that phosphorene is more sensitive to environmental variations.