Inexpensive and efficient catalysts which can promisingly operate under tolerant conditions are still urgently needed in the development of photocatalytic hydrogen evolution systems. Present work investigates the visible-light induced generation of bimetallic FeNi mixture with fluorescein (Fl) as photosensitizer in triethanolamine (TEOA) aqueous solution. FeNi NPs (NPs) in situ generated were found to be in intimate contact in the nano-mixture which upon formation performs as catalysts for photocatalytic hydrogen evolution in the same system under air atmosphere. Under bright LED light irradiation, the system with FeNi produced more than three times hydrogen than systems with same molar amount of single Fe or Ni component. Importantly, about two-fold higher hydrogen production activity compared with noble metal Pt catalyst under air atmosphere was observed. The work exhibited an economic and effective means of harnessing cheap bimetallics for tackling photocatalytic hydrogen evolution reactions. The mechanistic insights governing the photocatalytic processes and the factors leading to the enhanced hydrogen evolution activity were discussed. (C) 2015 Elsevier B.V. All rights reserved.