In this work, the effect of varying the size of the precursor raw materials SiO2 and ZrO2 in the solid-state synthesis of NASICON in the form Na3Zr2Si2PO12 was studied. Nanoscale and macro-scale precursor materials were selected for comparison purposes, and a range of sintering times were examined (10, 24 and 40 h) at a temperature of 1230 degrees C. Na3Zr2Si2PO12 pellets produced from nanopowder precursors were found to produce substantially higher ionic conductivities, with improved morphology and higher density than those produced from larger micron-scaled precursors. The nanoparticle precursors were shown to give a maximum ionic conductivity of 1.16 x 10(-3) S cm(-1) when sintered at 1230 degrees C for 40 h, in the higher range of published solid-state Na3Zr2Si2PO12 conductivities. The macro-precursors gave lower ionic conductivity of 0.62 x 10(-3) S cm(-1) under the same processing conditions. Most current authors do not quote or consider the precursor particle size for solid-state synthesis of Na3Zr2Si2PO12. This study shows the importance of precursor powder particle size in the microstructure and performance of Na3Zr2Si2PO12 during solid-state synthesis and offers a route to improved predictability and consistency of the manufacturing process.