Abstract Functional building blocks (fullerene and fluorene) were integrated into multilayers by utilizing electrochemical coupling layer-by-layer (ECC-LbL) assembly driven by the covalent carbon–carbon coupling reaction of pendant alkylcarbazoyl groups. The ECC-LbL assembly in patterning mode can be used to locally immobilize functional units and has been demonstrated here in a patterned fluorescent display. ECC-LbL is a versatile method for surface fabrication with promising potential in many applications.