Additive manufacturing of ceramics through the direct ink writing method becomes possible when the effective parameters on rheology are optimized accurately. Successful manufacturing first requires the easy flowing of the ink through the nozzle and then a suitable viscoelastic response for the shape retention of the 3D printed structure. In the present study, fused silica pastes with different particle size distributions varying from D90 of 5–50 µm were prepared for direct ink writing of porous structures. The rheological properties of the pastes, including flow behavior and the viscoelastic moduli variations, were investigated to study the influence of particle size and its distribution on fabricating complex structures. Through investigations, it was found that the narrower size distributions were more appropriate for direct ink writing of fused silica pastes. As the distribution became narrow, the shear thinning behavior was intensified, and the pastes showed high elasticity. The sintering procedure was performed using microwave radiation to suggest a fast process for manufacturing fused silica complex parts containing partially crystallized cristobalite phase and providing porosity of about 10% and a relative density of 90%.