This review provides an overview of some important investigations performed on the development of efficient electrocatalysts in the presence of alkaline solutions. The efficient electrocatalysts must encounter different characteristics such as low overpotential for hydrogen evolution reaction (HER), good catalytic activity, high stability and low cost. This review provides basic information, particularly about the development and properties of some of the most investigated electrocatalysts, namely from the iron group elements (iron, nickel or cobalt). A great interest to investigate amorphous alloys can be found in literature because of their superior properties towards HER. Amorphous alloys show many interesting properties such as electrochemical and good mechanical properties along with high corrosion resistance. Molybdenum and phosphorous, as most promising elements offering great amorphization capability, were widely investigated in the literature. The induced co-deposition of molybdenum and phosphorous was particularly considered in this review. Other metal groups such as pure metals, some rare-earth elements etc. were also discussed as alloyed composites. A focus was made on electrodeposition method used for the alloys preparation, especially for chlor-alkali industry applications. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.