In the process of molecular modification on an electrode surface, the unspecific adsorption of molecules impedes preparation of ordered molecular interface. In this study, we have investigated the unspecific adsorption of a designed molecule for photo-excited current based affinity sensors on a semiconductor electrode. In preparation process of the molecular interface, we propose an unspecific-adsorption-free process using cyclodextrin, which is able to suppress unspecific molecular adsorption at the solution-solid interface. Using the method, specific reaction of molecular immobilization can be done without disturbance of the unspecific adsorption.