Electroreduction of nitrate (NO 3 RR) to ammonia in membraneless electrolyzers is of great significance for reducing the cost and saving energy consumption. However, severe chemical crossover with side reactions makes it challenging to achieve ideal electrolysis. Herein, we propose a general strategy for efficient membraneless ammonia synthesis by screening NO 3 RR catalysts with inferior oxygen reduction activity and matching the counter electrode (CE) with good oxygen evolution activity while blocking anodic ammonia oxidation. Consequently, screening the available Co-Co system, the membraneless NO 3 - -to-NH 3 conversion performance was significantly higher than H-type cells using costly proton-exchange membranes. At 200 mA cm -2 , the full-cell voltage of the membraneless system (∼2.5 V) is 4 V lower than that of the membrane system (∼6.5 V), and the savings are 61.4 kW h (or 56.9%) per 1 kg NH 3 produced. A well-designed pulse process, inducing reversible surface reconstruction that in situ generates and restores the active Co(III) species at the working electrode and forms favorable Co 3 O 4 /CoOOH at the CE, further significantly improves NO 3 - -to-NH 3 conversion and blocks side reactions. A maximum NH 3 yield rate of 1500.9 μmol cm -2 h -1 was achieved at -0.9 V (Faraday efficiency 92.6%). This pulse-coupled membraneless strategy provides new insights into design complex electrochemical synthesis.