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Ammonia (NH3) is a cornerstone widely used in the modern agriculture and industry, the annual global production gradually increases to almost 200 million tons. Nearly 80% of the produced NH3 is used in the fertilizer industry and is essential for the development of global agriculture and consequently for maintaining population growth. Furthermore, NH3 can power hydrogen (H2) fueled devices, such as H2 fuel cells (FC), to use the interconversion between chemical energy and electric energy of nitrogen (N2) cycle, which can effectively alleviate the intermittent problems of renewable energy. However, the problems faced by NH3 in storage and release still restrict its development. Herein, this review introduces the latest research and development of electrochemical NH3 synthesis and direct NH3 FC, as well as outlines the technical challenges, possible improvement measures and development perspectives. N2 reduction reaction (NRR) and nitrate reduction reaction (NO3−RR) are two potential approaches for electrochemical NH3 synthesis. However, the existing research foundation still faces challenges in achieving high selectivity and efficiency. Direct NH3 FC are easy to transport and are expected to be widely used in mobile energy consuming equipment, but also limited by the lack of highly active and stable NH3 oxidation electrocatalysts. The perspectives of ammonia fuel cells as an alternative green energy are discussed.