A new concept of designing and synthesizing highly dispersed ionic liquids was developed through physical confinement or encapsulation of them into silica gel matrix with sol-gel process. A series of silica gel confined ionic liquids were synthesized through this process and characterized by diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS) and FTRaman analysis, and abnormal FT-IR and FTRaman spectra were observed. The silica gel matrixes confined ionic liquid BMImBF(4) were further characterized by BET analysis after the ionic liquid was almost completely washed out by acetone under refluxing conditions and meso-porous silica gel matrixes were obtained according to the N(2) adsorption measurements, which suggested that the particle-size of the dispersed ionic liquids was in nano-scale. In consideration of the results obtained together, it could be found that the abnormal FT-IR and FTRaman spectra were changed with the pore-size of the silica gel matrix. For example, obvious abnormal FT-IR and FTRaman spectra appeared when the particle-size of ionic liquid BMImBF(4) is smaller than 11 nm while they disappeared again if the corresponding particle-size >11 nm. These results indicated that nano-effect, or restriction effect, produced from the nano-pores of silica gel was the reason for the abnormal FT-IR and FTRaman spectra.