3D-architectured　graphene　is　an　emerging　electrode　material　because　of　its　ultra-low　mass　density　and　hierarchically　connective　pore-structure,　which　can　provide　a　large　accessible　surface　area　and　also　enhance　mass　and　electron　transport.　However,　few　reports　are　concerned　with　the　fundamental　electrochemical　study　of　this　fascinating　material.　In　this　work,　we　prepared　reduced　graphene　oxide　aerogel　(RGOA)　samples　by　thermal　reduction　of　the　original　graphene　oxide　aerogel　(GOA)　at　different　temperatures　and　comparatively　studied　their　structure　and　fundamental　electrochemical　performance.　By　using　three　representative　inner-　and　outer-sphere　redox　probes,　we　found　that　RGOA,　which　was　reduced　at　250　°C　outperforms　its　analogues　by　providing　the　lowest　ΔEp　as　well　as　the　highest　k　0.　This　is　due　to　its　abundant　accessible　active　sites,　which　can　effectively　interface　with　electrolytes,　facilitate　electron　transfer,　and　provide　multiplexed　and　highly　conductive　pathways.　In　contrast　to　2D-structured　graphene,　the　electrochemical　performance　of　3D-architectured　graphene　is　influenced　by　not　only　the　amount　of　oxygen-containing　groups　and　structural　defects,　but　also　by　the　macropores　and　surface　roughness,　which　enhance　hydrophilicity/hydrophobicity.　The　as-constructed　RGOA-based　sensor　shows　good　sensitivity　and　selectivity　for　the　detection　of　dopamine.　This　study　adds　a　new　dimension　to　the　electrochemical　performance　and　applications　of　3D-architectured　graphene.　©　2014　the　Partner　Organisations.