for HER when nanoscale MoS 2 is used, [ 1 ] albeit bulk MoS 2 is suggested to be inactive towards HER. [ 2 ] Thus most studies have focused on designing thin layered/nanostructured MoS 2 nanomaterials with most exposed edges for HER. To this end, amorphous MoS 2,[ 3 ] MoS x nanosheets [ 4 ] were found to outperform bulk MoS 2 signifi cantly; layer-dependent attributes, [ 5 ] the correlation with intrinsic low conductivity out-of-plane, and phasedetermined performance have also been studied. [ 6 ] These fi ndings have stimulated the work of sulfi de of earth-abundant metals, e.g., WS 2 [ 7 ] and its analogues, selenides, [ 8 ] resulting in a big family of chalcogenides of fi rst-row transition metals. [ 9 ] Reviews [ 6b , 7c , 10 ] have been conducted from different perspectives and can be referred to accordingly. Unfortunately, the best performing MoS 2 catalyst still lacks the competitiveness of Pt. Furthermore, improvements in performance relies heavily on the basis that moly bdenum/tungsten chalcogenides (sulfi de, selenide) are nanostructured with abundant S-edges and are thin layered (preferable single layer). These requirements may severely constrain their application in large-scale production. Thus, it is imperative to continue the search for new inexpensive catalysts that can rival the performance of Pt while being suitable for large-scale hydrogen production.It was only recently discovered that hydrogen evolution proceeds via a similar pathway to that of hydrogenation (hydrotreating process), e.g., hydrodesulfurization (HDS), where a reversible ad/desorption of hydrogen on catalyst is critical for achieving fast kinetics. This correlation broadens the scope of search for new catalysts. Hence, phosphides, previously employed as catalysts for HDS, were found to be active towards HER, e.g., Ni 2 P [ 11 ] has been reported to achieve a better performance than the state-of-the-art MoS 2 .[ 11c ] This pivotal work [ 11c ] was followed by a variety of studies applying phosphide as catalysts for HER. This class of electrocatalyst with superb electrocatalytic activities has thus opened up a new avenue in the search of non-noble metal catalysts for HER. Here, we focus our discussion on the recent developments of synthesis methodology of phosphides for HER. Based on different synthetic routes of phosphides, we then make a comparative survey of their activities, which are evaluated in terms of experimental metrics of over-potential ( η ) at a certain current density ( j ), Tafel slope coupled with exchange current density ( j o ) extrapolated from the plot of η vs. Log 10 ( j ), and turnover frequency (TOF). In conjunction with experimental results, Hydrogen evolution by means of electrocatalytic water-splitting is pivotal for effi cient and economical production of hydrogen, which relies on the development of inexpensive, highly active catalysts. In addition to sulfi des, the search for non-noble metal catalysts has been mainly directed at phosphides due to the superb activity of phosphides for hydrogen ev...