Polyurea elastomers are utilized for a myriad of applications ranging from coatings and foams to dielectric materials for capacitors and actuators. However, current synthetic methods for polyureas rely on highly reactive isocyanates, solvents, and catalysts, which collectively pose serious safety considerations. This report details the synthesis and characterization of melt processible, poly(tetramethylene oxide) (PTMO)-based segmented polyurea elastomers utilizing an isocyanate-, solvent-, and catalyst-free approach. Dynamic mechanical analysis and differential scanning calorimetry suggested microphase separation between the hard and soft segments. Tensile analysis revealed high strain at break for all segmented copolymers between 340 and 770%, and tunable modulus between 0.76 and 29.5 MPa. Dielectric spectroscopy revealed that the composition containing 20 wt% hard segment offered the highest permittivity at 10.6 (1 kHz, 300 K) of the segmented copolymers, indicating potential as a dielectric elastomer.