Spin valves are key to spintronics but are typically limited to engineered thin-film heterostructures. Achieving intrinsic spin-valve-like behavior in bulk materials would mark major progress toward scalable spintronics. Here, we report a multiprobe study of the quaternary Heusler alloy CoFeVSb, a rare multifunctional "quantum composite" combining spintronic, thermoelectric, and topological properties. Neutron powder diffraction confirms long-range magnetic order at low temperature and the coexistence of antiferromagnetic (AFM) and ferromagnetic (FM) components due to partial ${\mathrm{DO}}_3$ disorder, forming AFM/FM interfaces and spin pinning at room temperature. Magnetotransport measurements reveal robust asymmetric magnetoresistance at room temperature—a hallmark of spin-valve behavior usually seen in multilayers. Hard x-ray photoemission spectroscopy (HAXPES) resolves the valence-band structure, consistent with density-functional theory (DFT) calculations and confirming a metallic nature. HAXPES further shows that structural disorder stabilizes AFM/FM coexistence, giving rise to the spin-valve-like magnetoresistance. By correlating structure, magnetism, and transport, this work demonstrates intrinsic spin-valve functionality, establishing CoFeVSb as a strong candidate for scalable, multifunctional spintronic platforms.

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• Heusler alloy
• Spin valves
• Ab initio calculations
• Hard x-ray photoelectron spectroscopy
• Neutron diffraction