Manipulation structure of graphitic carbon nitride (GCN) to tune its photophysical and interfacial redox activity is one of fundamental issues for understanding and improving its photocatalytic hydrogen evolution (PHE) activity. In this work, we report our recent progress on manipulating structure of GCN via an easy and effective approach. Trace level iron is found to have increased atomic concentration and tuned bond state of carbon in structure manipulated GCN (M-GCN) along with porosity of it, which exhibits higher interfacial redox and photophysical activity than GCN. The improved interfacial redox and photophysical activities of M-GCN are found to have synthetic enhanced consumption of photo-generated electrons and holes during photocatalysis process and reduction of their recombination, which results in promotion of its PHE activity. PHE rate for M-GCN is found to be 2286 mu mol(-1) g h(-1), which is 2.82 time of GCN.