Flexible/foldable, self-supporting, porous, and wearable bifunctional fabrics for sunlight heating and phase change temperature control are designed and constructed for wearable thermal management. In this study, coaxial fibers with polyvinylidene fluoride polymer solution uniformly doped with Cu₇S₄ as sheath and n-eicosane as core components are fabricated by electrospinning technology. Remarkably, based on the fast solar-to-thermal conversion of the photothermal conversion material, the as-obtained fabric provides sunlight heating for an extra warmth of 25 °C within 1.5 min. Besides, active temperature control via fabric internal phase transformation reduces the daily temperature fluctuations, which is superior to that of the normal and traditional cotton fiber. Impressively, the present bifunctional fabric possesses both better thermal comfortability, including breathability, sweat wicking, and stain resistance, and high durability against wash and soak over 120 h, suggesting its great potential in wearable technologies for thermal regulation.