Thermal transport across inorganic/organic interfaces attracts interest from both academia and industry due to their wide applications in flexible electronics, etc . Here, the interfacial thermal conductance of inorganic/organic interfaces consisting of silicon and polyvinylidene fluoride is systematically investigated using molecular dynamics simulations. Interestingly, it is demonstrated that a modified silicon surface with hydroxyl groups can drastically enhance the conductance by 698%. These results are elucidated based on interfacial couplings and lattice dynamics insights. This study not only provides feasible strategies to effectively modulate the interfacial thermal conductance of inorganic/organic interfaces but also deepens the understanding of the fundamental physics underlying phonon transport across interfaces.