The blending of polyolefins (POs), such as polyethylene (PE) and polypropylene (PP), is a growing area of research, particularly for recycling mixed polyolefin (MPO) waste through flotation sorting techniques. However, understanding the thermomechanical behavior of these recycled blends is challenging due to limitations in the existing characterization methods. This paper introduces a combined experimental and numerical method to accurately assess the complex mechanical behavior of high-density PE, PP, and their blends. We conducted detailed thermomechanical analyses using a high-speed stereo digital image correlation (DIC) system paired with an infrared camera to capture temperature variations alongside mechanical stress and strain. This approach allowed us to correct for distortions caused by necking and to derive accurate stress–strain relationships. We also applied a cutting-edge unified semi-crystalline polymer (USCP) model to simplify the analysis, focusing on the effects of strain rate and temperature, including self-heating and thermal softening phenomena. Our results, which closely match experimental observations of stress–strain behavior and temperature changes, offer new insights into the thermomechanical properties of PO blends, which are essential for advancing their practical applications in various fields.