Retention behaviors of various planar and non-planar polycyclic aromatic hydrocarbons (PAHs), and all carbon compounds so-called fullerenes with 2,4,6-(tri-tert-butylphenoxy)dimethyl (TBP) silica phase and benzyldimethyl (Benzyl) silica phase have been investigated using microcolumn liquid chromatography system. The results clearly indicate that these phases possess a “non-planarity” recognition capability of PAHs. Non-planar solutes were retained longer than planar ones with these phases under certain separation conditions, although the opposite trend where the planar solutes are retained longer than the non-planar ones was observed with typical octadecylsilica (ODS) phases. This unique behavior can be explained by the specific molecular-molecular interaction between non-planar solutes and the stationary phase moiety having a cavity like structure made by the three tert-butyls and phenyl ring of the moiety. The separation of C60and C70were also examined and the difference of the structural uniqueness between TBP phase and Benzyl phase showed interesting results for such bulky fullerenes separation.