Inspired by the intriguing nature of the metal-π interaction in organometallic chemistry, a novel 1D hybrid material has been designed. Herein, a functionalized tellurium allyl macrocycle (TAM) acts as a molecular building block and is knit together via silver-π interaction to obtain Ag-TAM. Ag is coordinated to two allyl groups and a phenyl ring in η2 mode. Instead of the conventional polymerization strategy, a metal-π interaction is employed to interlink macrocycles. TAM and Ag-TAM showed electrocatalytic capability for the conversion of nitrate to ammonia. Ag-TAM showed an NH3 yield rate 2-fold greater than TAM with a high faradaic efficiency of 94.6% with good durability, proving that interlinking of macrocycles via metal-π interaction improves the catalytic activity. Detailed periodic density functional theory (DFT) calculations unveil novel mechanistic insights, suggesting cooperative catalysis between neighboring Ag sites and contributing to the enhanced efficiency.