Cost-efficient　material　with　an　ingenious　design　is　important　in　the　engineering　applications　of　flexible　energy　storage　and　electromagnetic　(EM)　protection.　In　this　study,　bimetallic　ZnCo2S4　(ZCS)　polyhedral　nanoparticles　homogenously　embedded　in　the　surface　of　porous　N-doped　carbon　nanofiber　membranes　(ZCS@PCNFM)　have　been　fabricated　by　electrospinning　technique　combined　with　carbonization　and　hydrothermal　processes.　As　a　self-assembled　electrode　for　lithium-ion　batteries　(LIBs),　the　bimetallic　ZCS　nanoparticles　possess　rich　redox　reactions,　good　electrical　conductivity,　and　pseudocapacitive　properties,　while　the　three-dimensional　(3D)　multiaperture　architecture　of　the　nanofiber　film　not　only　shortens　the　transfer　spacing　of　lithium　ions　and　electrons　but　also　effectively　tolerates　the　volume　variation　during　lithiation　and　delithiation　cycles.　Benefiting　from　the　above　merits,　the　ZCS@PCNFM　electrode　exhibits　good　cycle　performance　(662.3　mA　h/g　at　100　mA/g　after　100　cycles),　superior　rate　capacity　(401.3　mA　h/g　at　1　A/g)　and　an　extremely　high　initial　specific　capacity　of　1152.2　mAh/g　at　100　mA/g.　Meanwhile,　depending　on　the　hierarchical　nanostructure　and　multi-component　heterogeneous　interface　effects　constructed　by　3D　inlaid　architecture,　the　ZCS@PCNFM　nanocomposite　exhibits　fascinating　microwave　absorption　(MA)　characteristics　with　a　superhigh　reflection　loss　(RL)　of　-49.7　dB　at　a　filling　content　of　only　20　wt%　and　corresponding　effective　absorption　bandwidth　(EAB,　RL＜-10　dB)　of　5.2　GHz　ranging　from　12.8　to　18.0　GHz　at　2.2　mm.