The　increasing　demand　for　higher-energy-density　batteries　driven　by　advancements　in　electric　vehicles,　hybrid　electric　vehicles,　and　portable　electronic　devices　necessitates　the　development　of　alternative　anode　materials　with　a　specific　capacity　beyond　that　of　traditional　graphite　anodes.　Here,　the　state-of-the-art　developments　made　in　the　rational　design　of　Si-based　electrodes　and　their　progression　toward　practical　application　are　presented.　First,　a　comprehensive　overview　of　fundamental　electrochemistry　and　selected　critical　challenges　is　given,　including　their　large　volume　expansion,　unstable　solid　electrolyte　interface　(SEI)　growth,　low　initial　Coulombic　efficiency,　low　areal　capacity,　and　safety　issues.　Second,　the　principles　of　potential　solutions　including　nanoarchitectured　construction,　surface/interface　engineering,　novel　binder　and　electrolyte　design,　and　designing　the　whole　electrode　for　stability　are　discussed　in　detail.　Third,　applications　for　Si-based　anodes　beyond　LIBs　are　highlighted,　specifically　noting　their　promise　in　configurations　of　Li–S　batteries　and　all-solid-state　batteries.　Fourth,　the　electrochemical　reaction　process,　structural　evolution,　and　degradation　mechanisms　are　systematically　investigated　by　advanced　in　situ　and　operando　characterizations.　Finally,　the　future　trends　and　perspectives　with　an　emphasis　on　commercialization　of　Si-based　electrodes　are　provided.　Si-based　anode　materials　will　be　key　in　helping　keep　up　with　the　demands　for　higher　energy　density　in　the　coming　decades.　©　2021　Wiley-VCH　GmbH