In this paper, a novel concept in the field of phase composite ceramics has been proposed and applied for creating the topcoats of durable thermal barrier coatings (TBCs), which is one of the most critical technologies for advanced high-efficiency gas turbine engines in extreme environments. The phase composite ceramic TBCs were designed to demonstrate superior and comprehensive performance-related merits, benefits, and advantages over conventional single-phase TBCs with a topcoat of 8YSZ or Gd2Zr2O7, including thermal phase stability, thermal shock durability, low thermal conductivity, and solid particle erosion resistance. In this paper, we review and summarize the development work conducted so far related to the phase composite ceramic concept, coatings processing, and experimental investigation into TBC behaviors at elevated temperatures (typically, ≥1250 °C) using different evaluation and characterization methods, including isothermal sintering, a burner rig test, a solid particle-impinging erosion test, and a CMAS corrosion test. Two-phase (t’+c) zirconia-based TBCs demonstrated improved thermal shock and erosion resistance in comparison to conventional single-phase (t’), 8YSZ TBC, and Gd2Zr2O7 TBC, when used separately. Additionally, a triple-phase (t’+c+YAG) TBC sample demonstrated superior CMAS resistance. The TBC’s damage modes and failure mechanisms for thermal phase stability, thermal cycling resistance, solid particle erosion behavior, and CMAS infiltration are also characterized and discussed in detail, in terms of microstructural characterization and performance evaluation.