Multifunctional materials that integrate optical and electric properties into a single composite have tremendous research value and application prospects for future optoelectronic devices. Meanwhile, the enhancement of luminescent performances of active materials through modulation of the microstructure has triggered the development of high-performance photonic devices. In this work, the nanocrystal embedded composite was fabricated to investigate their luminescent properties with and without compositional change. The results show that both the introduction of an impurity and the application of an electric field results in the enhancement of photoluminescence in this hybrid system. The observed phenomena can be ascribed to the modification of the environment around Er3+ by different approaches. The samples prepared in this work have proven to possess luminescent and electric properties simultaneously, and the light amplification caused by the polarizing process offers a novel approach in glass systems to enhance infrared photoluminescence without compositional change, which will make this kind of material more competitive in the optoelectronics field.