Cationic cyclopentadienyliron complexes of chloro-substituted arenes were found to perform efficient Pd-catalyzed cross-coupling reactions with arylboronic acids under mild conditions. Using this method, some new cationic cyclopentadienyliron complexes of biaryl derivatives (Fc-Bi) were obtained with good yields. After a photolysis reaction of the obtained Fc-Bi, some biaryl derivatives were easily obtained. Results in the present study provided a practical route to the preparation of Fc-Bi and biaryl derivatives.