ever-increasing requirement for high energy density, [1][2][3][4] especially when incorporating with further material modification through nanocomposites, [7][8][9][10] blending, [11][12][13][14][15][16] laminated structure, [17][18][19][20][21] cross-linking, [22,23] and so on.Nevertheless, the state-of-the-art PVDF-based ferroelectric polymer usually exhibits mediocre temperature stability in energy storage performance, which cannot fully satisfy the applications at elevated temperature caused by the energy consumption or nearby heat sources. [24][25][26] These polymers commonly possess glass transition temperature (T g ) far below room temperature (as shown in Table S1, Supporting Information), which helps to enhance the energy density but sacrifices temperature stability. The molecular motion in ferroelectric polymers can be activated above T g , which promotes polar molecules orientation under external stimulus evidenced by a sudden increase of permittivity at T g . [23,27] Consequently, ultrahigh energy density (about 4-35 J cm −3 ) for PVDF-based polymers has always been reported at room temperature above T g . [1][2][3] On the other hand, low T g is detrimental to temperature stability of energy storage in PVDF showing dramatical degradation at elevated temperatures. Because rubbery-state amorphous region above T g , which manifests itself as loose chains with increased free volume, becomes vulnerable to temperature rise. [25,26,28] Recent investigations even point out that high-T g non-ferroelectric polymers can maintain an energy density around 0.5-1.8 J cm −3 up to a fairly high temperature. [25,26,29] Nonetheless, for ferroelectric polymers, it remains a considerable challenge to achieve high energy storage performance at the elevated temperature.In this work, we propose to design a strategy for stabilizing high energy density of ferroelectric polymer (PVDF) over a wide temperature range by blending with a miscible high-T g polymer (polymethyl methacrylate [PMMA]). The blending material forms a alternating lamellar structure consisting of high-polarization crystalline regions and mixed amorphous regions. It is found that this special morphology can induce a spatial confinement effect of chain mobility and structural change at elevated temperatures. Accordingly, the associated Thermal stability of polymer structure is a key to achieve stable energy density at elevated temperature for ferroelectric-polymer-based capacitors. Here, a poly (vinylidene fluoride) / polymethyl methacrylate (PMMA) blend with a stabilized spherulite structure displaying steady energy density around 7.8-9.8 J cm −3 across the temperature range up to 70 °C is reported, which outperforms most neat ferroelectric polymers at elevated temperature. The microstructure of the blend observed by atomic force microscopy exhibits an alternating lamellar structure (crystalline/mixed amorphous layers) within spherulites, which might be rationalized by PMMA being gradually expelled from the spherulite and finally staying between PVDF lamellae ...