Optimization of electrospun TiO2/CuO composite nanofibers shows that TiO2/CuO composite nanofibers with 6 mol.% Cu, calcined at 450 degrees C for 45 min, exhibited the highest H-2 generation from 10% (v/v) methanol aqueous solution. The significance of balance and synergy among the essential physicochemical properties such as morphology, porosity, specific surface area, degree of crystallinity, crystal size, as well as elemental states on the photocatalytic H-2 generation of electrospun TiO2/CuO composite nanofibers was further revealed by means of varying the synthesis calcinations temperatures. Calcinations at temperature above and below 450 degrees C showed negative effect on the H-2 generation. This was ascribed to the temperature effect on transformation of crystalline phase, crystal growth, mesoporosity formation, and Cu valence state which has thus adversely affected the synergy among the physicochemical properties governing the photocatalytic activity of TiO2/CuO composite nanofibers. Good stability with negligible Cu leaching and reusability were also attained with the composite nanofibers. This study serves as a significant advancement platform to designing and fabricating high efficient and stable TiO2/CuO composite nanofibers via facile electrospinning thus promoting its application potential as an economical photocatalyst for production of clean energy. (C) 2013 Elsevier B.V. All rights reserved.