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Single-crystal thiophene-phenylene (TPCO) and furan-phenylene co-oligomers (FPCO) have a great potential for the application in optoelectronics and photonic devices, since they can combine high luminescence and efficient charge transport. The promising approach to control the luminescent properties of organic semiconductor crystals is their doping by highly luminescent molecules. Recently, we have found that these luminescent dopant molecules can appear as byproducts in the course of TPCO chemical synthesis. In this work, we report on study of luminescent dopants in single-crystal TPCO and FPCO. Photothermal deflection spectroscopy, which can probe very low amount of impurities via their absorption in the transparency range of the material. The TPCO and FPCO crystals were grown from the vapor phase and from solution. We detected the dopant absorption features in the TPCO and FPCO single crystals samples.