Highly conductive polymer fibers are key components in the design of multifunctional textiles. Measuring the voltage/temperature relationships of these fibers is very challenging due to their very small diameters, making it impossible to rely on classical temperature sensing techniques. These fibers are also so fragile that they cannot withstand any perturbation from external measurement systems. We propose here, a non-contact temperature measurement technique based on fiber Bragg gratings (FBGs). The heat exchange is carefully controlled between the probed fibers and the sensing FBG by promoting radiation and convective heat transfer rather than conduction, which is known to be poorly controlled. We demonstrate our technique on a highly conductive Poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS)-based fiber. A non-phenomenological model of the sensing system based on meaningful physical parameters is validated towards experimental observations. The technique reliably measures the temperature of the polymer fibers when subjected to electrical loading. © 2015 IOP Publishing Ltd.