Polymer electrolyte coated carbon fibres embedded in polymeric matrix materials represent a multifunctional material with several application scenarios. Structural batteries, thermal management materials as well as stiffness adaptive composites, made from this material, are exposed to significant joule heat, when electrical energy is transferred via the carbon fibres. This leads to a temperature increase of up to 100 K. The thermal behaviour of this composite material is characterized in this numerical study based on a RVE representation for the first time. Compared to classical fibre reinforced plastics, this material comprises a third material phase, the polymer electrolyte coating, covering each individual fibre. This material has not been evaluated for effective thermal conductivity, specific heat and thermal behaviour on the microscale before. Therefore, boundary conditions, motivated from applications, are applied and joule heating by the carbon fibres is included as heat source by an electro-thermal coupling. The resulting temperature field is discussed towards its effect on the mechanical behaviour of the material. Especially the temperature gradient is pronounced in thickness direction, leading to a temperature drop of 1∘Cmm, which needs to be included in thermal stress analysis in future thermo-mechanically coupled models. Another important emphasis is the identification of suitable homogenization and model reduction strategies in order to reduce the numerical effort spent on the thermal problem. Therefore, traditional analytical homogenization methods as well as a newly proposed “Two-Level Lewis-Nielsen” approach are discussed in comparison to virtually measured effective quantities. This extensive comparison of analytical and numerical methods is original compared to earlier works dealing with PeCCF composites. In addition, the accuracy of the new Two-Level Lewis-Nielsen method is found to fit best compared to classical methods. Finally, a first efficient and accurate 2D representation of the thermal behaviour of the PeCCF composite is shown, which reduces computational cost by up to 97%. This benefit comes with a different Temperature drop prediction in thickness direction of 1.5∘Cmm. In the context of future modelling of multifunctional PeCCF composite materials with multiphysical couplings, this deviation is acceptable with respect to the huge benefit for computational cost.