Electrocorticography (ECoG) has garnered widespread attention owing to its superior signal resolution compared to conventional electroencephalogram (EEG). While ECoG signal acquisition entails invasiveness, the invasive rigid electrode used inevitably inflicts damage on brain tissue. Polymer electrodes that combine conductivity and transparency have garnered great interest because they not only facilitate high-quality signal acquisition but also provide additional insights while preserving the health of the brain, positioning them as the future frontier in the brain-computer interface (BCI). This review summarizes the multifaceted functions of polymers in ECoG thin-film electrodes for the BCI. We present the abilities of sensitive and structural polymers focusing on impedance reduction, signal quality improvement, good flexibility, and transparency. Typically, two sensitive polymers and four structural polymers are analyzed in detail in terms of ECoG electrode properties. Moreover, the underlying mechanism of polymer-based electrodes in signal quality enhancement is revealed. Finally, the remaining challenges and perspectives are discussed.