To achieve ionic liquids (ILs) that show fast solute diffusivity independent of viscosity domination, sixteen ILs containing Si or Si-O-Si groups (SiILs) were synthesized. Diffusion coefficients of three solute molecules with different molecular sizes, i.e., CO, diphenylacetylene, and diphenylcyclopropenone, were determined in SiILs using the transient grating method and the results were compared to other solvent system. SiILs showed distinguishably faster diffusivity for the smallest solute, CO, than conventional ILs at the same viscosity, particularly in the high viscosity region. Based on previous results and our estimation, three plausible factors exists that contribute to the faster solute diffusivity in SiILs, i.e., the flexibility of the Si or Si-O-Si group, decreased interaction between the cation and the solute, and increased free volume because of the bulky structure.