Radioluminescent batteries, characterized by their high energy density and long lifespan, are ideal power sources for wireless sensor networks and micro-electromechanical systems. However, their practical application has been hindered by the inherent low energy conversion efficiency. Herein, we quantified the energy loss modes in RL batteries and demonstrated the corresponding efficiency enhancing strategies. A Monte Carlo model incorporating the coupled effects of the radiation and optical fields was first developed and revealed that the optical loss is accounting for around 75% in x-ray RL batteries. Reflective layers and optocoupler adhesive layers are employed and improve significantly the optical coupling efficiency from 23.6% to 51.7%, resulting in a 225% overall performance enhancement of CsI: Tl-based RL batteries. This study not only highlights the critical role of optical field engineering in boosting RL batteries performance but also provides insights to unlock the full potential of RL batteries.