Structural variation in alumina directly determines the thermal stability of transition alumina with La dopant at high temperature. In this work, the thermal stability and alumina structure from well-crystallized ultrafine boehmite doped with various La-bearing compounds were studied. La2O3, LaAlO3, and LaAl11O18 could not efficiently inhibit transition alumina changing into alpha-Al2O3, alpha-Al2O3 seed benefited alpha-Al2O3 formation in the presence of La dopant. La(NO3)(3) doping into boehmite effectively improved the thermal stability of theta-Al2O3 above 1200 degrees C. The nano-diameter active spots with low melting point led to the formation of alpha-Al2O3 with a smooth edge and sintering neck from the blank boehmite, whereas La dopant contributed to rhombus theta-Al2O3 with considerable pores, jagged edge, and wedge at 1200 degrees C for 2 h. Moreover, the Al and La contents fluctuated asynchronously during calcination, and the atomic ratio of Al/O decreased with the addition of La dopant. These results are attributed to La migration, assembling in active spots and increasing their melting point. Furthermore, relative to nearly 100% AlO6 coordination in alpha-Al2O3, La dopant significantly increased the AlO4 content above 900 degrees C. Therefore, La dopant increased the melting point of the active spots, hindered AlO6 formation, and inhibited alpha-Al2O3 nucleation on the alumina surface, thereby improved the thermal stability of the transition alumina. (C) 2020 Elsevier B.V. All rights reserved.