We have developed a novel route for the synthesis of high-performance bio-polyimides (PIs) microbially-derived from photo-responsive aromatic diamine 4,4'-diaminostilbene (DAS) and its reduced counterpart 4, 4'-(ethane-1,2-diyl) dianiline (EDDA). DAS and EDDA were condensed with various commercially-available dianhydrides to obtain a series of poly(amic acid)s (PAAs) and PIs which were characterized in terms of their thermal, mechanical, and photo-functions. These bio-based PAAs showed a very high viscosity of 6.62 dL/g, and the PIs showed ultrahigh thermal resistance with T-d10 values over 600 degrees C, which were higher than that of any bio-based plastic reported thus far. They also showed T-g values above 250 degrees C, and tensile strength of over 132 MPa, which is higher than that of Kapton (TM). The PIs also showed photo-functional behavior based on stilbene-based photoreactions. (C) 2015 Elsevier Ltd. All rights reserved.