In　this　work,　a　Sn　nanoparticle　(NP)/carbon　nanofiber　(CNF)　hybrid　with　unique　structure　has　been　designed　and　fabricated　via　electrospinning　and　subsequent　heat　treatment.　The　cell　assembled　by　the　binder-free　Sn　NP/CNF　hybrid　demonstrates　an　effective　capacity　(46　mAh　g(-1)　at　200　mA　g(-1)　after　200　cycles)　with　high　coulombic　efficiency　(up　to　99.8%),　suggesting　a　facile　strategy　for　the　scalable　fabrication　of　electrochemically　stable　electrodes　for　LIBs.　For　understanding　the　electrochemical　behaviors　of　the　metallic　Sn　and　carbon　nanofibers　in　the　lithiation/delithiation　process,　in　situ　transmission　electron　microscopy　was　applied　to　study　the　single　hybrid　structure.　In　the　first　charge/discharge　process,　real-time　size　variation　of　the　Sn　NP　and　CNFs　was　mainly　focused,　suggesting　a　two-step　lithiation　process　in　the　metallic　Sn　NP.　Structural　characterization　also　indicates　an　irreversible　delithiation　in　a　single　Sn　NP/CNF　hybrid　structure.　The　electrochemical　performance　based　on　influence　of　carbonization　temperature　has　also　been　discussed.　The　results　and　fundamental　understanding　of　the　lithiation/delithiation　in　the　Sn-based　hybrid　anodes　enables　the　communities　to　design　flexible　high-performance　electrodes　based　on　metallic　active　materials　in　a　rational　way.　(C)　2014　Elsevier　Ltd.　All　rights　reserved.