Control over charge transfer, energy or electron transfer process in a donor-acceptor system israther significant for organic electronics. Although, numerous reports emphasize the balancing between thestrength of donor and acceptor direct the specific phenomenon, however, stimuli-responsive D-A system arevery few till now. Thereby, we have selected the thianthrene and porphyrin as an electron donor and acceptorfor designing the D-A systems and investigated their physico-chemical properties under external stimuli.Herein, free base and metalated thianthrene-porphyrin-based derivatives such as P-TA and P_Zn-TA weredesigned and synthesized by using Suzuki coupling reaction followed by metalation. Photophysical analysisof two derivatives in chlorinated solvents revealed that charge transfer complex formation whilst applicationof light as an external stimulus. Cyclic voltammetry studies depict the ease of oxidation suggests that efficientelectron transfer from donor to acceptor via CT complex. Therefore, these results promote the design of novelthianthrene based D-A systems for organic light-emitting diode applications.