• A multi-scale conductive network was constructed in flexible PDMS/Ag@PLASF/CNT composite with micro-size Ag@PLASF and nano-size CNT.

• The PDMS/Ag@PLASF/CNT composite showed outstanding electrical conductivity of 440 S m^-1 and superior electromagnetic interference shielding effectiveness of up to 113 dB.

• The PDMS/Ag@PLASF/CNT composites owned good retention (> 90%) of electromagnetic interference shielding performance even after subjected to a simulated aging strategy or 10,000 bending-releasing cycles.

Highly conductive polymer composites (CPCs) with excellent mechanical flexibility are ideal materials for designing excellent electromagnetic interference (EMI) shielding materials, which can be used for the electromagnetic interference protection of flexible electronic devices. It is extremely urgent to fabricate ultra-strong EMI shielding CPCs with efficient conductive networks. In this paper, a novel silver-plated polylactide short fiber (Ag@PLASF, AAF) was fabricated and was integrated with carbon nanotubes (CNT) to construct a multi-scale conductive network in polydimethylsiloxane (PDMS) matrix. The multi-scale conductive network endowed the flexible PDMS/AAF/CNT composite with excellent electrical conductivity of 440 S m⁻¹ and ultra-strong EMI shielding effectiveness (EMI SE) of up to 113 dB, containing only 5.0 vol% of AAF and 3.0 vol% of CNT (11.1wt% conductive filler content). Due to its excellent flexibility, the composite still showed 94% and 90% retention rates of EMI SE even after subjected to a simulated aging strategy (60 °C for 7 days) and 10,000 bending-releasing cycles. This strategy provides an important guidance for designing excellent EMI shielding materials to protect the workspace, environment and sensitive circuits against radiation for flexible electronic devices.

• 采用微米尺寸Ag@PLASF和纳米尺寸CNT，在柔性PDMS/Ag@PLASF/CNT复合材料中构建了多尺度导电网络。

• ^{PDMS/Ag@PLASF/CNT复合材料表现出出色的440 S m -1}电导率和高达113 dB的优异电磁干扰屏蔽效能。

• 即使经过模拟老化策略或 10,000 次弯曲释放循环后，PDMS/Ag@PLASF/CNT 复合材料仍具有良好的电磁干扰屏蔽性能保留率（> 90%）。

具有优异机械柔韧性的高导电聚合物复合材料（CPC）是设计优异电磁干扰（EMI）屏蔽材料的理想材料，可用于柔性电子设备的电磁干扰防护。制造具有高效导电网络的超强 EMI 屏蔽 CPC 迫在眉睫。本文制备了一种新型镀银聚丙交酯短纤维（Ag@PLASF，AAF），并将其与碳纳米管（CNT）集成，在聚二甲基硅氧烷（PDMS）基质中构建多尺度导电网络。^{多尺度导电网络赋予柔性PDMS/AAF/CNT复合材料440 S m −1}的优异电导率和高达113 dB的超强EMI屏蔽效能（EMI SE），仅含有5.0 vol%的AAF和3.0 vol% CNT（11.1wt% 导电填料含量）。由于其优异的柔韧性，即使经过模拟老化策略（60°C，7天）和10,000次弯曲释放循环后，该复合材料仍表现出94%和90%的EMI SE保留率。该策略为设计优异的 EMI 屏蔽材料提供了重要指导，以保护工作空间、环境和敏感电路免受柔性电子设备的辐射。