Sequential　paired　electrosynthesis　capable　of　the　production　of　organic　chemicals　through　a　series　of　electrochemical　reactions　that　occur　consecutively　and　in　pairs　are　of　high　significance.　Herein,　a　three-dimensional　porous　carbon　felt-loaded　PbO2　electrode　(PbO2/CF)　with　a　self-supported　nanostructure　was　fabricated　using　a　double-cathode　electrodeposition　method,　which　served　as　an　efficient　electrocatalyst　enabling　the　unique　sequential　paired　electrosynthesis　of　1,4-hydroquinone　(1,4-HQ)　from　phenol　in　a　membrane-free　electrolytic　cell.　In　such　an　exotic　paired　electrolysis　system,　phenol　is　first　oxidized　to　p-benzoquinone　at　the　anode,　which　is　subsequently　reduced　to　1,4-HQ　at　the　cathode.　The　as-obtained　PbO2/CF　electrode　exhibited　a　remarkable　electrochemical　performance,　achieving　impressive　conversion　and　selectivity　of　94.5%　and　72.1%,　respectively,　for　the　conversion　of　phenol　to　1,4-HQ.　This　exceptional　performance　can　be　attributed　to　the　open　porous　self-supported　structure　of　the　PbO2/CF　electrode,　which　improves　the　active　site　exposure　and　substrate　adsorption　capability　and　reduces　mass　and　charge　transfer　resistance.　Furthermore,　the　catalyst　electrode　well　maintained　its　structure　integrity　even　after　140　hours　of　long-term　use,　further　highlighting　its　promising　application　for　the　electrosynthesis　of　1,4-HQ.　Moreover,　this　sequential　paired　electrosynthesis　strategy　can　be　further　extended　to　other　substrates　with　electron-withdrawing/donating　groups　over　the　PbO2/CF　electrode.　The　proof　of　concept　in　this　innovative　sequential　paired　electrosynthesis　could　provide　a　sustainable　and　efficient　way　to　produce　various　desired　organic　compounds.Keywords:　Phenol;　1,4-Hydroquinone;　Electrocatalysis;　Sequential　paired　electrosynthesis;　Self-supported　electrodes.