Ionic conductivity of solid polymer electrolytes (SPEs) can be enhanced by the addition of fillers, while maintaining good chemical stability, and compatibility with popular cathode and anode materials. Additionally, polymer composite electrolytes can replace the flammable organic liquid in a lithium-ion battery design and are compatible with lithium metal. Compatibility with Li-metal is a key development towards a next-generation rechargeable Li-ion battery, as a Li-metal anode has a specific capacity an order of magnitude higher than LiC6 anodes used today in everyday devices. The addition of fillers is understood to suppress the crystalline fraction in the polymer phase, increasing the ionic conductivity, as Li-ion conduction is most mobile through the amorphous phase. A full model for a conduction mechanism has not yet constructed, as there is evidence that a semi-crystalline PEO-based electrolyte performs better than a fully amorphous electrolyte. Furthermore, it is not yet fully understood why the weight load of fillers in PCEs can range from 2.5%wt to 52.5%wt, in order to achieve high ionic conductivity (~10-4S/cm). This work seeks to investigate the conduction mechanism in the PCE through the use of doped-Li7La3Zr2O12 as a filler and analysis of the PCE microstructure. In this work, a solid-state electrolyte, doped-Li7La3Zr2O12 (LLZO) was synthesized via a sol-gel method, and characterized. The effect of doping and co-doping the Li, La and Zr sites in the LLZO garnet was investigated. A PEO-based polymer composite electrolyte (PCE) was prepared by adding bismuth doped LLZO (Li7-xLa3Zr2-xBixO12) as a filler. The bismuth molar ratio was changed in value to study the dopant role on the bulk PCE ionic conductivity, polymer phase crystallinity and microstructure. Results suggest that small variations in dopant can determine the optimal weight load of filler at which the maximum ionic conductivity is reached. By understanding the relationship between filler properties and electrochemical properties, higher performance can be achieved with minimal filler content, lowering manufacturing costs a solid-state rechargeable Li-ion battery.