The nucleation threshold of nanobubble formation around the surface of nanoparticles with small sizes is significantly high under the irradiation of incident light, which has limited their applications in the fields of optofluidics and biomedicine. To solve this problem, nanoparticles are assembled into an array to investigate the generation process of nanobubbles around them under the impact of the localized surface plasmon resonance (LSPR)-induced enhanced electric field (EEF) by using molecular dynamics (MD) simulations and continuum equations. The results of MD simulations indicate that even if the nanoparticle temperature is close to the melting point, it is still difficult to generate nanobubbles around the surface of an individual nanoparticle with a radius of 2 nm. However, when nanoparticles are assembled into an array, the progressive nucleation and generation process of nanobubbles around their surface can be observed after a thermal diffusion process lasting approximately 1050 ps. When the LSPR effect is excited, water molecules can be rapidly transformed from the liquid state to the gaseous state under the perturbation of an intensive EEF, which can further promote the generation process of nanobubbles. Moreover, using the thermal diffusion equation with a modification of the interfacial thermal resistance, a detailed analysis is also conducted for the phase change process of the water region surrounding nanoparticles under the effect of the LSPR-induced EEF. Compared with the results of MD simulations, it can be observed that the modified thermal diffusion equation can clearly demonstrate the initial nucleation of nanobubbles around the surface of a nanoparticle array but the size of the generated nanobubble is slightly smaller. On this basis, the generation process of nanobubbles can be flexibly manipulated by adjusting the gap distance of an array, the number of nanoparticles in an array, and the polarization direction of the incident light. The results could provide a new approach to investigate the nucleation and generation process of nanobubbles, which makes them more attractive in various emerging applications.