The global population explosion and accelerated industrialization have led to an increasing shortage of fossil fuels and environmental contamination, underscoring the urgent need to develop innovative energy storage technologies to improve energy utilization efficiency. As pivotal components in thermal energy storage (TES) systems, phase change materials (PCMs) enable spatiotemporal matching between thermal energy supply and demand through latent heat absorption and release during phase transitions. Organic PCMs are considered ideal candidates for thermal energy storage due to their high energy storage density, stable phase transition temperature, low supercooling, and negligible phase separation. However, inherent drawbacks such as low thermal conductivity, liquid leakage, limited light absorption, and lack of functionality have hindered their widespread application in advanced thermal management systems. Herein, we systematically summarize cutting-edge functionalization strategies for PCMs, progressing from conventional methods like thermal conductive particle blending and microencapsulation to the emerging design of 3D porous thermally conductive skeletons, including metal foams, boron nitride aerogels, carbon-based aerogels, and MXene aerogels. These frameworks not only enhance thermal transport via continuous conductive pathways and impart shape stability through capillary encapsulation but also, when integrated with photo-thermal, electro-thermal, and magneto-thermal conversion properties, enable broad applications in solar photo-thermal/photo-thermo-electric conversion, thermal management of electronics and batteries, building efficiency, and wearable thermal regulation. The review further addresses current challenges and future directions, highlighting scalable 3D framework fabrication, the shift to active thermal management, and innovative applications beyond conventional domains. By establishing a microstructure–property–application correlation, this work provides valuable insights for developing next-generation high-performance multifunctional phase change composites.

The orientation of amorphous regions in pure polymers has been noted to be critical to the enhancement of thermal conductivity (TC), but the available reports are still rather few. Here, we propose to prepare a polyvinylidene fluoride (PVDF) film with a multi-scale framework by introducing anisotropic amorphous nanophases in the form of cross-planar alignments among the in-planar oriented extended-chain crystals (ECCs) lamellae, which show an enhanced TC of 1.99 $\mathrm{W}{\mathrm{m}}^{-1} {\mathrm{K}}^{-1}$ in the through-plane direction ($K_{\perp }$) and 4.35 $\mathrm{W}{\mathrm{m}}^{-1} {\mathrm{K}}^{-1}$ in the in-plane direction ($K_{\parallel }$). Structural characterization determination using scanning electron microscopy and high-resolution synchrotron X-ray scattering showed that shrinking the dimension of the amorphous nanophases can effectively reduce entanglement and lead to alignments formation. Moreover, the thermal anisotropy of the amorphous region is quantitatively discussed with the aid of the two-phase model. Superior thermal dissipation performances are intuitively displayed by means of finite element numerical analysis and heat exchanger applications. Moreover, such unique multi-scale architecture also results in significant benefit in the improvement of dimensional stability and thermal stability. This paper provides a reasonable solution for fabricating inexpensive thermal conducting polymer films from the perspective of practical applications.