Electrocatalytic technology is one of the most attractive technologies for renewable energy storage and conversion, and nano-scale noble metals exhibit excellent electrocatalytic activity. However, because of the scarcity of precious metal resources and high development costs, reducing the dosage of precious metals while improving activity and durability of catalysts is always the research focus in the field of catalysis applications. Among various candidates, noble metal phosphide-based new electrocatalysts have received widespread attention due to their multifunctional active sites, adjustable structure and composition, and unique physical and chemical properties. Compared with transition metal phosphide, noble metal phosphides have higher intrinsic activity, and exhibit better stability under acid condition. In this review, the research progress of noble metal phosphides was mainly summarized including design synthesis, structural engineer, X-ray absorption spectroscopic characterization, and electrocatalytic applications. Eventually, the current challenges and opportunities for the development of noble metal phosphide-based electrocatalysts were discussed, along with the future prospection of in situ synchrotron radiation X-ray characterizations that might be applied in this field.