Polystyrene with triptcyene units were synthesized by combination of Atom Transfer Radical Polymerization (ATRP) and oClicko chemistry processes and characterized. Well-defined precursor polystyrene with predetermined molecular weight and narrow polydispersity was prepared by ATRP in the presence of Cu(I)/pentamethyldiethylenetriamine (PMDETA) catalyst system and terminal bromine groups of the obtained polymer were converted to azide group by using NaN3. The click reaction between diazido compounds, namely diazido polystyrene (N3-PSt-N3) and diazidodecane (DAD) and dialkyne compounds, dipropargyloxytriptycene (DPT) and dipropargyloxydecane (DPD) resulted in the formation polystyrene with triptycene units in the main chain. Dialkyne compound without triptycene unit such as dipropargyloxybenzene (DPB) was used under the same click conditions for comparison. Characterization of the intermediates and the resulting polymers was performed by means of FT-IR and 1H-NMR spectral analysis, and GPC, DSC and TGA studies. The effect of the triptycene moiety on the thermal properties was evaluated.