<P><B>Abstract</B></P> <P>Simultaneous dark fermentative hydrogen and ethanol production from waste bread in a mixed packed tank reactor (MPTR) was investigated. Waste bread was first hydrolyzed by the produced enzymes to generate the waste bread hydrolysate which was subsequently introduced to the MPTR for dark fermentative hydrogen and ethanol production. The optimal hydrogen and ethanol production rates were 15.01 mmol/(h·L) and 23.25 mmol/(h·L) when the organic loading rate reached 32 g/(L·d). The unit hydrogen and ethanol production were 4.87 mmol hydrogen/g waste bread and 7.54 mmol ethanol/g waste bread, respectively. This study provided a new direction for economic and efficient hydrogen and ethanol production from waste bread.</P> <P><B>Highlights</B></P> <P> <UL> <LI> We develop a novel bioprocess for fermentative hydrogen and ethanol production. </LI> <LI> Enzymatic hydrolysis could release glucose and free amino acid from waste bread. </LI> <LI> Unit hydrogen and ethanol production were 4.87 mmol/g bread and 7.54 mmol/g bread. </LI> </UL> </P>