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Abstract Near‐infrared (NIR) absorbing electron donor‐acceptor (D−A) chromophores have been at the forefront of current energy research owing to their facile charge transfer (CT) characteristics, which are primitive for photovoltaic applications. Herein, we have designed and developed a new set of benzothiadiazole (BTD)‐based tetracyanobutadiene (TCBD)/dicyanoquinodimethane (DCNQ)‐embedded multimodular D−A systems (BTD1‐BTD6) and investigated their inherent photo‐electro‐chemical responses for the first time having identical and mixed terminal donors of variable donicity. Apart from poor luminescence, the appearance of broad low‐lying optical transitions extendable even in the NIR region (>1000 nm), particularly in the presence of the auxiliary acceptors, are indicative of underlying nonradiative excited state processes leading to robust intramolecular CT and subsequent charge separation (CS) processes in these D−A constructs. While electrochemical studies identify the moieties involved in these photo‐events, orbital delocalization and consequent evidence for the low‐energy CT transitions have been achieved from theoretical calculations. Finally, the spectral and temporal responses of different photoproducts are obtained from femtosecond transient absorption studies, which, coupled with spectroelectrochemical data, identify broad NIR signals as CS states of the compounds. All the systems are found to be susceptible to ultrafast (~ps) CT and CS before carrier recombination to the ground state, which is, however, significantly facilitated after incorporation of the secondary TCBD/DCNQ acceptors, leading to faster and thus efficient CT processes, particularly in polar solvents. These findings, including facile CT/CS and broad and intense panchromatic absorption over a wide window of the electromagnetic spectrum, are likely to expand the horizons of BTD‐based multimodular CT systems to revolutionize the realm of solar energy conversion and associated photonic applications.