The Zr-rich(Zr0.8Ti0.2)B2 and the Ti-rich(Ti0.8Zr0.2)B2 solid solutions are formed when TiB2 and ZrB2 are hot-pressed.To forecast the properties of the two solid solutions,their valence electron structure was analyzed based on the empirical electron theory(EET) of solids and molecules.We used three different models,the average atom model,the average cell model and the real cell model,and compared with the calculation results from the three models.In the real cell model,the lattice constants of the solid solu-tions were supposed to be changed or unchanged.The results showed that different models could only result in slight change in the hybridization levels of the metal atoms in the two solid solutions and little difference between the calculation values.However,they can not change the variant trend of the va-lence electron structure nor the properties of the solid solutions.Thus,the three models and the methods are appropriate and the calculation results are reasonable and consistent. The Zr-rich (Zr0.8Ti0.2) B2 and the Ti-rich (Ti0.8Zr0.2) B2 solid solutions are formed when TiB2 and ZrB2 are hot-pressed. To the properties of the two solid solutions, their valence electron structure was analyzed based on the empirical electron theory (EET) of solids and molecules. We used three different models, the average atom model, the average cell model and the real cell model, and compared with the calculation results from the three models. In the real cell model, the lattice constants of the solid solu-tions were supposed to be changed or unchanged. The results showed that different models could only result in slight change in the hybridization levels of the metal atoms in the two solid solutions and little. difference between the calculation values.However, they can not change the variant trend of the va-lence electron structure nor the properties of the solid solutions.Thus, the three models and the methods are appropriate and the calculation results are reasonable and consistent.