Monolayer graphene has attracted enormous attention owing to its unique electronic and optical properties. However, achieving an effective approach without applying electrical bias for manipulating the charge transfer based on graphene is elusive to date. Herein, we realized the manipulation of excitons’ transition from emitter to the graphene surface with plasmonic engineering nanostructures and firstly obtained large enhancements for photon emission on the graphene surface. The localized plasmons generated from the plasmonic nanostructures of shell-isolated nanoparticle coupling to ultra-flat Au substrate would dictate a consistent junction geometry while enhancing the optical field and dominating the electron transition pathways, which may cause obvious perturbations for molecular radiation behaviors. Additionally, the three-dimensional finite-difference time-domain and time-dependent density functional theory were also carried out to simulate the distributions of electromagnetic field and energy levels of hybrid nanostructure respectively and the results agreed well with the experimental data. Therefore, this work paves a novel approach for tunning graphene charge/energy transfer processes, which may hold great potential for applications in photonic devices based on graphene.