Cation radical salts of BEDO-TTF (BO) with six kinds of polycyano counter anions of tetracyanoallyl derivatives (R-TCA; R: substituent) were investigated. Although the stoichiometries of the salts are different from salt to salt, the degree of charge transfer on BO molecules ranges from +0.4 to +0.5. 2-propoxy-TCA anion (PrO-TCA) provides a semiconducting salt, while the other anions afford metallic ones, The EtO-TCA(-) salt exibits successive metal-semiconductor and semiconductor-metal transitions near 150 K and 40 K, respectively. Magnetic susceptibility of this salt shows slight decrease near 100 K and it keeps non-zero value even at 1.9 K. The crystal structures of three kinds of the salts were solved. The salts of EtO-TCA- and cyanomethyl(CM)-TCA(-) have I-3-type packing motifs of the BO molecules. The salt of DHCP2- (R = C(CN)C(CN)C(CN)(2)(-)) has a similar packing motif to I-3-type, however, the stacking direction of the BO molecules varies par five BO molecules.