The valorization of straw waste as a sustainable and eco-friendly resource in polymer composites is critical for resource recycling and environmental preservation. Therefore, many research works are being carried out regarding the development of wheat straw-based polymer composites to identify the reinforcing potential of these sustainable resources. In this study, three different sizes of wheat straw fibers (60–120 mesh, 35–60 mesh, and 18–35 mesh) were used, and their different ratios (0, 2.5, 5, 10, and 20% by weight) were systematically investigated for the physical and mechanical properties of polypropylene-based sustainable composites. The results indicated that the evaluated composites’ properties are strongly dependent on the quantity and size of the utilized wheat straw. Therefore, a preference selection index was applied to rank the developed sustainable polymer composites to select the best composition. Various properties of the composite materials were considered as criteria for ranking the alternatives, namely tensile strength and modulus, flexural stress at conventional deflection and flexural modulus, impact strength, density, water absorption, material cost, and carbon footprint. The decision-making analysis suggests the alternative with wheat straw content of 20 wt.% (35–60 mesh size) dominating the performance by maximizing the beneficial criteria and minimizing the non-beneficial criteria, making it the most suitable alternative. This study will significantly help formulation designers to deal with the amount and size issues when developing polymeric composites.