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Electrocatalytic nitrogen reduction reaction (NRR) is a complementary route to the traditional Haber‐Bosch process. Boosting the reaction kinetics of electrocatalytic NRR is key to promote the NH₃ yield. Herein, we demonstrate that the confinement of reactive intermediates (e. g., *N₂) in highly ordered blue TiO₂ nanotubes (b‐TiO₂) can significantly enhance the surface reaction rate of electrocatalytic NRR on the encapsulated metal oxide catalysts. The enhancement of the reaction rate of NH₃ synthesis is attributed to the increased surface coverage of intermediates inside the b‐TiO₂ nanotubes. Benefiting from the confinement effect of intermediates, the b‐TiO₂ nanotubes enclosing metal oxide electrodes show both higher production rate and Faradaic efficiency of NH₃ than the combined ones of individual metal oxide and b‐TiO₂ electrodes.