In this work, the oxidation behavior of an atmospheric plasma-sprayed thermal barrier coating (TBC) system with a thin Al physical vapor deposition (PVD) film deposited over the bond coat is discussed. The TBC consisted of: (i) CoNiCrAlY bond coat sprayed on the Inconel 600 substrate; (ii) a thin Al interlayer deposited by direct current DC magnetron sputtering; and (iii) yttria-stabilized zirconia (YSZ) sprayed as the top coat. Such thermal barrier coatings (Al-TBC) were isothermally oxidized at 1150 °C with different holding times, and then they were compared with the reference TBC (R-TBC) systems without an Al interlayer (R-TBC). Scanning electron microscopy with energy-dispersive X-ray analysis was used to study the oxide formation along the bond coat (BC) and top coat (TC) interface, as well as crack formation in the yttria-stabilized zirconia top coat. Then, using Image Analysis, the oxide formation and crack formation were characterized in all specimens after a slow heating and cooling cycle, and after 100, 300, and 600 h of isothermal exposure. The results showed that the Al-TBC system proposed here exhibits higher oxidation resistance at the bond coat and top coat interface, less crack formation in the YSZ top coat, and enhanced mechanical stability compared to the conventional TBCs. It was found that enrichment of the bond coat and top coat interface with Al limited the formation of detrimental transition metal oxides during isothermal loading. Finally, the corresponding failure caused by thermally grown oxide (TGO) phenomena is “mixed failure mode” for both studied TBCs.