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[Display omitted] • The concept of a stimuli-activated molecular dopant (SAMD) strategy is introduced. • As a proof of concept, selected photoacid generators are examined as the SAMD and devised photoactivated acidic doping. • The results demonstrate superior thermoelectric properties with high molecular order retained after doping. Conjugated polymers (CPs) are a promising class of materials for organic thermoelectric generators (OTEGs); however, achieving high electrical conductivity through molecular doping while maintaining compatibility with thin-film printing processes remains a huge challenge. In this paper, we present a novel doping strategy using stimuli-activated molecular dopants (SAMDs) based on photoacid generators (PAGs) that can be activated by light of a specific wavelength. We demonstrate that this approach can effectively control the doping efficiency and optoelectronic properties of CP-PAG-blended thin films, resulting in a wide range of electrical conductivities. Our selected PAG molecules enabled efficient printing of the CP-PAG mixed solution and yielded a high thermoelectric figure of merit. To elucidate the mechanism behind this high thermoelectric performance, we systematically investigated the morphologies, microstructures, and energy structures of the PAG-doped CP thin films and performed various comparative tests. We also demonstrate the feasibility of using SAMDs to print flexible OTEG modules on thin polyimide substrates. We believe that our work represents a significant step toward the development of efficient, scalable, and sustainable thermoelectric devices for power generation and waste heat recovery, and highlights the advantages of PAG-based SAMDs for printable organic thermoelectrics. [ABSTRACT FROM AUTHOR]