Microwave ultra-wideband (UWB) radar systems are advantageous for their high-range resolution and ability to penetrate dielectric objects. Internal imaging of dielectric objects by UWB radar is a promising nondestructive method of testing aging roads and bridges and a noninvasive technique for human body examination. For these applications, we have already developed an accurate internal imaging approach based on the range points migration (RPM) method, combined with a method that efficiently estimates the dielectric constant. Although this approach accurately extracts the internal boundary, it is applicable only to highly conductive targets immersed in homogeneous dielectric media. It is not suitable for multi-layered dielectric structures such as human tissues or concrete objects. To remedy this limitation, we here propose a novel dielectric constant and boundary extraction method for double-layered materials. This new approach, which simply extends the Envelope method to boundary extraction of the inner layer, is evaluated in finite difference time domain (FDTD)-based simulations and laboratory experiments, assuming a double-layered concrete cylinder. These tests demonstrate that our proposed method accurately and simultaneously estimates the dielectric constants of both media and the layer boundaries.