Cell attachment onto electrode-forming biocathodes is a promising alternative to expensive catalysts used for electricity production in bioelectrochemical systems (BESs). Though BESs have been extensively studied for decades, the processes, underlying mechanisms, and determinant driving forces of microalgal biocathode formation remain largely unknown. In this study, we employed a model unicellular motile microalga, Chlamydomonas microsphaera, to investigate the microalgal attachment processes onto the electrode surface of a BES and to identify the determinant factors. Results showed that the initial attachment of C. micrrosphaera cells is determined by the applied external voltage rather than nutrient availability and occurs via electrotaxis-mediated cell motility. The subsequent development of the C. microsphaera biofilm is then increasingly determined by nutrient availability. Our results revealed that, in the absence of an external voltage, nutrient availability remains a dominant factor controlling the fate of the microalgal surface attachment and subsequent biofilm formation processes. Thus, our results show that electrotactic and chemotactic movements are crucial to facilitate the initial attachment and subsequent biofilm formation of C. microsphaera onto the electrode surfaces of BES. This study provides new insights into the mechanisms of microalgal surface attachment and biofilm formation processes on microalgal biocathodes, which hold great promise for improving the electrochemical properties of cathodes.