In this communication, a novel synthetic pathway has been applied to prepare a dual imaging agent in a single molecule. The dinuclear Re(I)/Tc(I) complex 6, namely [Re(CO)(3)(bipy){(4-PyrIDA)Tc(CO)(3)}], is the first example of a Re/Tc-based heterometallic assembly which could act as a potential bimodal Optical/SPECT probe. Interestingly, the Re(I) complex intermediate 4 exhibits significant photophysical properties for biological applications.