Development of flexible Li–S batteries brings along the flourishing prospective for energy‐hungry wearable devices. However, it is still seriously restricted due to lack of facile methods to solve its inherent problems and flexible device‐related current collection issues. Herein, quasi‐stable electroless deposition method is firstly proposed to solve these problems by fabricating 3D tunable Ni–P networks in the C/S free‐standing electrode. The ultrathin Ni–P layers which are highly conductive and strongly adhesive with electrode substrates improve the electronic conductivity by two orders of magnitude and rise initial specific capacity from 1200 to 1600 mAh g−1. The harmful shuttle effect of polysulfide is also effectively alleviated due to the chemical adsorption and physical sieving properties of the 3D networks. The flexible pouch Li–S batteries assembled with commercially applicable structure also show high flexibility and as high as 1420 mAh g−1 output capacity at 0.1C in cycling test. This method can definitely be extended to other flexible devices such as Li‐ion batteries, Li–O2 batteries, and supercapacitors.

Paper Link：https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.201707272