In the present work, varying silica nanofillers (SiO2) compositions were successfully introduced into PMMA/PLA-20%LiBOB amorphous gel polymer electrolyte (GPE) systems. FTIR analysis unveiled subtle alterations in wavenumber shifting and intensity at several highlighted peaks, indicating the occurrence of molecular interactions within the GPE. XRD analysis revealed a notable reduction in crystallinity, particularly up to 6 wt.% SiO2, implying that the presence of nanofillers influenced complexation ability and amplified amorphous regions. Meanwhile, TGA analysis confirmed that the 6 wt.% SiO2 sample exhibited the least mass loss, affirming its exceptional thermal stability and proved the increase in ionic conductivity until the maximum value of 2.19×10-3 S cm-1 for samples up to 6 wt.%. The TNM testing resulted in a notably high lithium-ion transference number, which indicates the practical viability of this composition for application in lithium-ion batteries and provides promising enhanced electrochemical performance.