The structure of Nd0.75Sm0.25GaO3 was studied by high-resolution powder diffraction methods using conventional x-ray and synchrotron radiation in the temperature range 85-1173 K. The GdFeO3 structure type was confirmed for Nd0.75Sm0.25GaO3 in the temperature region investigated and no structural transitions were observed. The cell parameters show a monotonic and anisotropic increase with temperature. The interatomic potential was fitted using the GULP code. Using this potential, a self-consistent approximation following the Debye model was constructed from the elastic constants of the crystals. The total phonon DOS, its projections onto atomic species, heat capacity Cv, Grüneisen parameter γ and thermal expansion coefficient α were considered in the framework of quasiharmonic lattice dynamics and the Debye model. The shape of the phonon DOS calculated from lattice dynamics differs significantly from the respected Debye DOS. The rare earth, gallium and oxygen atoms dominate in different frequency regions of the phonon spectrum. The heat capacity is well reproduced by the Debye model below 100 K, where acoustic phonons play an important role and above 800 K when the classical limit is reached. Predicted values of Grüneisen parameter and thermal expansion coefficients in the frame of the Debye model are ∼35% too low. Therefore, the thermal properties of Nd0.75Sm0.25GaO3 cannot be explained by acoustic phonons only and hence, Nd0.75Sm0.25GaO3 cannot be described perfectly as a Debye-like solid with respect to its thermodynamic properties.