Hydrogen production from water splitting is considered as a brand-new and promising way to convert solar energy into recyclable chemical energy. Herein, a core-shell-shaped structure which consisted of Mn0.05Cd0.95S nanorods and flowerlike NiAl-LDH microsphere was constructed via a simple hydrothermal method. The constructed Mn0.05Cd0.95S/ NiAl-LDH core-shell-shaped structure shows superior photocatalytic H(2)evolution. The highest photocatalytic H(2)evolution rate of the composite is 7.5 mmol g(-1) h(-1), which is 17 and 6 times higher than those of NiAl-LDH and Mn0.05Cd0.95S respectively. The core-shell like structure is beneficial for the H(2)production reaction because NiAl-LDH flowerlike microsphere can provide large surface for the anchoring of Mn0.05Cd0.95S nanorods, which can enhance the interaction between these two materials. A series of characterizations including XRD, FT-IR, SEM, TEM, BET, XPS, UV-vis DRS, etc., were conducted and studied to analyze the reason for the enhanced photocatalytic hydrogen evolution activity. The results of XPS show that an interaction between NiAl-LDH and Mn0.05Cd0.95S has been occurred. The interaction between these two materials is presented through the transfer of electrons, which can be demonstrated by the results of XPS. And, it is found that the rational designed structure can accelerate the transfer of electrons and this is the reason for the enhanced photocatalytic evolution performance. Graphic A core-shell like structure consisted of Mn0.05Cd0.95S nanorods and NiAl-LDH nanoflower like sphere was designed rationally via a simple method. The NiAl-LDH nanoflower like sphere with some wrinkles on its surface can provide more areas to contact with Mn0.05Cd0.95S nanorods, which can is beneficial for the interaction between these two materials and accelerate the transfer of electrons.