Bimetal-organic-framework (Bi-MOF) NH 2 -MIL-125(Ti/Cu)-derived nanocomposites are systematically investigated to elucidate the role of individual species TiO 2 , Cu x O and the porous carbon matrix in photocatalytic activity. Among the studied samples, the TiO 2 /Cu x O/C nanocomposite derived from heat processing NH 2 -MIL-125(Ti/Cu) under Ar/H 2 O vapor demonstrates the highest photocatalytic H 2 evolution performance due to the formation of a phasejunction between the wellcrystallized anatase/rutile TiO 2 polymorph, the optimized and codoped nitrogen/carbon in the composites, the formation of p−n heterojunctions between the TiO 2 and Cu x O nanoparticles, as well as their uniform distribution in a hydrophilic porous carbon matrix decorated with N and carboxylic functional groups. These parameters enable the in situ-formed multi-heterostructures in these nanocomposites to not only possess relatively narrower energy band gaps and improved spatial charge separation due to the formed type-II staggered p−n heterojunctions but also offer multiple pathways for charge diffusion, resulting in lower charge-transfer resistance, suppressed bulk charge recombination, and consequently, much improved visible-light absorption. Therefore, the Bi-MOF NH 2 -MIL-125(Ti/Cu)-derived TiO 2 /Cu x O/C nanocomposite provides easily accessible active sites with an excellent photocatalytic H 2 evolution activity of 3147 μmol g cat −1 h −1 , 99 times higher than that of bare TiO 2 . This work provides a simple one-step approach to producing tunable novel nanocomposites for efficient photocatalytic H 2 evolution without using expensive noble metals as cocatalysts.