Photosynthetic microrganisms, including cyanobacteria, can be interfaced with electrodes in biophotovoltaic devices (BPVs) for solar energy conversion. Effective BPV electrodes need to be conductive, transparent, flexible, biocompatible and environmentally friendly, while also being cost-effective, abundant in material and lightweight. The utilisation of electrically conducting polymers (CPs), particularly poly(3,4-ethylenedioxythiophene) (PEDOT) fabricated by an atmospheric pressure vapor phase polymerisation (AP-VPP) technique, is a promising avenue for BPV applications. However, challenges remain in optimising their performance as CPs are dynamic optoelectronic materials, and their interaction with photosynthetic biocatalysts under a range of conditions has not been explored thoroughly. Here we show that AP-VPP-PEDOT electrodes hold promise for interfacing with cyanobacteria in BPVs to generate green electricity under red and blue light and moderate applied potentials with exogenous electron mediators. The highest non-mediated photocurrent achieved was 0.48 µA cm⁻², with a two-layer PEDOT electrode at 0.5 V applied potential and blue light. The highest mediated photocurrent achieved was 2.73 µA cm⁻², with a one-layer PEDOT electrode at 0.3 V applied potential and blue light and the exogenous electron mediator 2,6-dichloro-1,4-benzoquinone (DCBQ). The proposed approach to fabricating PEDOT electrodes offers a new pathway for developing sustainable electrodes for BPVs and pinpoints strategies for future optimisation for achieving high-performance outcomes.