Bilayered thermal barrier topcoats have lead to a remarkable breakthrough in overcoming the disadvantages of the conventional yttria stabilized zirconia (YSZ) thermal barrier coatings (TBCs). The present work is devoted to studying the hot corrosion properties of two different bilayered ceramic topcoats, viz., (i) lanthanum cerium oxide with the formula La2Ce2O7 (LCO)/YSZ and LCO/cluster paired zirconia (gadolinia, dysprosia and yttria stabilized zirconia -(Gd,Dy,Y)SZ) plasma sprayed TBCs. Plasma spray grade YSZ and (Gd,Dy,Y)SZ are prepared by co-precipitation and solution combustion techniques as reported in the literature. The effect of thickness of the plasma sprayed top LCO layer in bilayered LCO/YSZ and LCO/(Gd,Dy,Y)SZ TBC systems under Type I hot corrosion condition is examined. The LCO/(Gd,Dy,Y)SZ bilayered coating with 100 μm LCO thickness exhibits better hot corrosion resistance than the LCO/YSZ system. The phase transformation of t′-ZrO2 to m-ZrO2 in LCO/(Gd,Dy,Y)SZ (100/150 μm) TBC is reduced markedly (60%) compared to LCO/YSZ (100/150 μm) TBC.