Conductive polymers facilitate the electrical current flow through the transfer of electrons and holes. They show promise for novel photo-functional materials in photovoltaics. However, substantial electrostatic interactions between electron donors and acceptors induce polymer aggregation, limiting moldability and conductivity. In this study, robust donor polymers with high heat resistance were synthesized by bonding triphenylamine (TPA) derivatives and formaldehyde to phenolic groups. Resulting TPA-based phenolic polymers exhibited flexible structures and fluorescence due to charge transfer with acceptor molecules. Furthermore, TPA-based phenolic polymers' capacity to distinguish acceptor molecule sizes correlated with their molecular weight, reflecting upon donor-acceptor interactions. This novel optical trait in phenolic polymers holds potential for electronic components and conductive materials.