The　ubiquity　of　solid-liquid　interfaces　in　nature　and　the　significant　role　of　their　atomic-scale　structure　in　determining　interfacial　properties　have　led　to　intensive　research.　Particularly　in　electrocatalysis,　however,　a　molecular-level　picture　that　clearly　describes　the　dynamic　interfacial　structures　and　organizations　with　their　correlation　to　preferred　reaction　pathways　in　electrochemical　reactions　remains　poorly　understood.　In　this　review,　CO2　electroreduction　reaction　(CO2RR)　is　spatially　and　temporally　understood　as　a　result　of　intricate　interactions　at　the　interface,　in　which　the　interfacial　features　are　highly　relevant.　We　start　with　the　discussion　of　current　understandings　and　model　development　associated　with　the　charged　electrochemical　interface　as　well　as　its　dynamic　landscape.　We　further　highlight　the　interactive　dynamics　from　the　interfacial　field,　catalyst　surface　charges　and　various　gradients　in　electrolyte　and　interfacial　water　structures　at　interfaces　under　CO2RR　working　conditions,　with　emphasis　on　the　interfacial-structure　dependence　of　catalytic　reactivity/selectivity.　Significantly,　a　probing　energy-dependent　“in　situ　characterization　map”　for　dynamic　interfaces　based　on　various　complementary　in　situ/operando　techniques　is　proposed,　aiming　to　present　a　comprehensive　picture　of　interfacial　electrocatalysis　and　to　provide　a　more　unified　research　framework.　Moreover,　recent　milestones　in　both　experimental　and　theoretical　aspects　to　establish　the　correct　profile　of　electrochemical　interfaces　are　stressed.　Finally,　we　present　key　scientific　challenges　with　related　perspectives　toward　future　opportunities　for　this　exciting　frontier.　©　2023　The　Royal　Society　of　Chemistry.