The application of microwave radiation for processing of glassy and semicrystalline thermoplastics, elastomeric polymers and composites was investigated. The goal of this research was to reveal the relationship between polymer structure and microwave absorptivity, and hence processability. The specimens were subjected to an electric field at 2.45 GHz either inside a rectangular waveguide or in a cylindrical resonant cavity applicator with less than 100 watts applied power. Both travelling wave modes and standing wave modes were examined. Temperatures, powers and times were recorded, leading to the concept of "microwave calorimetry." Low frequency dynamic mechanical and dielectric frequency-temperature spectra were obtained on the materials and combined to conveniently extrapolate structure-property relationships into the GHz region. A correlation was found between the dielectric properties of various polymers and the dipole moments of small molecule analogues. Evaluating heatability was most accurately found to be determined by the magnitude of (ε_S - ε_∞), the oscillator strength. The value of (ε_S - ε_∞) should be used together with the distribution of relaxation times and the activation energies of dipolar dispersion to predict heatability for microwave processing. The critical temperatures, T_C, of dielectric loss were obtained from the intercepts of positive slope tangents of heating rate versus temperature plots at 2.45 GHz for polymers. Microwave processing was rapid above the critical temperature where the maximum dielectric loss fell in the 2.45 GHz frequency domain for efficient coupling of energy to the polymers. Shifting the dielectric relaxation spectrum into the microwave region by directly or indirectly increasing the temperature of each sample was unique and of key importance to processability. A schematic model was proposed to explain the behavior of two-phase materials subjected to microwave heating. Combining the heatability, (ε_S - ε_∞), and the dielectric relaxation spectral response was found to be helpful in evaluating formulations of two-phase materials for electromagnetic radiation processing at high frequencies.