BaTi4O9 powders with improved crystal perfection and relatively large surface area were synthesized by the polymerized complex (PC) method calcined at reduced temperatures (700-1,000 degrees C) relative to the solid-state reaction (SSR) method. BaTi4O9 with a unique pentagonal-prism tunnel structure, combined with different cocatalysts (Pt, Ru, Ni, Cu, Co) as promoters, was investigated towards photocatalytic reactions for H-2 evolution from pure water and aqueous ethanol solution. Pt/BaTi4O9 achieved the highest activity from ethanol solution, and subsequently it was focused to study the effect of calcination temperature on photocatalytic activities. The maximum quantum yield for H-2 evolution from pure water and ethanol solution was obtained at 700 and 800 degrees C separately, with the value of 0.9% and 11.7% over Pt/BaTi4O9 photocatalysts.