The growing global population needs energy from clean and renewable resources to meet present and future demands. Ideally, green hydrogen is commonly considered the key to overcoming the energy problem and the future energy standard. One of the most promising technologies for the development of the hydrogen economy is electrolysis water splitting (WS) hydrogen (H2) production; nevertheless, developing highly efficient environmentally sustainable electrocatalysts remains a serious issue for this technology. Transition metals (TMs) have achieved substantial progress in recent years, as a structural-based electrocatalyst developing especially noteworthy attention for the hydrogen evolution process (HER). These features have been proven to constitute the perfect electrocatalyst due to their advantages such as low cost, efficiency, stability, a large number of active sites, and great surface. This comprehensive review explains TMs-based chalcogenides and particular structural arrangements of multi-dimensional (1D, 2D, and 3D) electrocatalysts on different substrates for WS hydrogen production. The reaction process, the importance of the electrocatalyst, the advantages of the structural materials, and the efficiency that fluctuates with phase dimensions, have been investigated. Finally, the present issues and prospects of structural materials for WS were investigated in terms of HER and the perspective of this field was presented.