New dianhydrides containing t-butyl and phenyl pendant groups have been synthesized and used as monomers, together with commercial diamines, to prepare novel polyimides. The influence of the chemical structure of the monomers on their reactivity has been studied by quantum semiempirical methods. The polyimides have been characterized by FTIR and by NMR in the case of soluble polymers. The presence of pendant groups and the method used to imidize polyimide precursors greatly affected polymer properties such as solubility, glass transition temperature, thermal stability, and mechanical properties. As a rule, the novel polyimides showed better solubility in organic solvents than the parent polyimides. Glass transition temperatures in the range 250-270 degrees C and decomposition temperatures over 520 degrees C were observed for the set of current polymers. Tensile strengths up to 135 MPa and mechanical moduli up to 3.0 GPa were measured on films of the current polyimides.