This work investigates the possibility of doping Si and Sn solid solution components (separate/simultaneous incorporation) into Ti3AlC2 to provide desired mechanical properties and tribological self-adaptability over a broad temperature range. The specimens are sintered at 1450 °C for 2 h in a vacuum environment with a pressure of 30 MPa. The phase composition, mechanical properties and tribological characteristics sliding against Al2O3 counter balls over a wide temperature range from room temperature to 800 °C are investigated. The results demonstrate considerable lattice distortion together with significant solid solution strengthening effects in quinary solid solutions. The friction coefficients of the four solid solutions are discovered to be temperature-sensitive from the distinguished variation tendencies in the wide temperature range. The wear rates exhibit a comparable tendency with test temperature that the values are two orders of magnitude lower at 600−800 °C than those at RT−400 °C. The noticeably lubricant tribofilm is responsible for the decreased wear rate at elevated temperatures. The distinct tribological behaviors of the quaternary and quinary solid solutions are ascribed to the characteristics of the self-generated oxides.