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Two‐photon Polymerization (2PP) process for high‐resolution 3D printing presents an opportunity to design micro‐scale structures with a high surface‐to‐volume ratio for highly responsive devices. However, these acrylate or thiol‐based resins are electrically insulating and non‐functional in nature, therefore limiting their widespread application in biosensing and biotechnology. Here, a novel conductive polymeric composite resin to print conductive 3D micro‐structures via the 2PP technique is developed and its application in sensing are demonstrated. The composite consists of acrylate‐based 2PP resin and Poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) (PEDOT:PSS), a conductive and biocompatible organic semiconductor The PEDOT:PSS incorporation in resin through Raman and X‐ray photoelectron spectroscopy (XPS) is studied. An electrical conductivity of 3.5 × 102 S cm−1 in a 20 µm long and 10 µm high 3D printed micro‐structure which is suitable for electronic applications is achieved. An ultra‐fast micro‐3D printed humidity sensor with a response and recovery time of 0.15 and 0.3 s respectively is demonstrated. The printed sensors show high sensitivity in humidity levels of 0–80%RH. As a proof of concept, the real‐time respiration of a human body is recorded, implying a potential application in health monitoring systems. [ABSTRACT FROM AUTHOR]