LaNi5 is an important material for hydrogen technology. LaNi5 nanofibers were synthesised for the first time by a sol-gel process via electrospinning in which polyvinylpyrrolidone was used as the spinning aid and lanthanum and nickel nitrate were used as precursors for the synthesis of LaNi5 nanofibers. X-ray spectrum studies of nanofibers prepared at different calcination temperatures showed a single phase and a hexagonal structure after hydrogen exposure. The temperature of calcination has a direct effect on the morphology and structure of nanofibers. The morphology of long nanofibers before and after calcination was studied by SEM. The high surface area of LaNi5 demonstrates the capability of nanofibers to serve as effective alloys in hydrogen storage applications. (C) 2012 Elsevier B. V. All rights reserved.