Selective and large-scale synthesis of [8]cycloparaphenylene (CPP) was achieved in seven steps starting from commercially available 4-bromo-4'-hydroxybiphenyl and 4,4'-dibromobiphenyl. The key unsymmetrical tetraring unit, 4-bromophenyl and 4'-bromobiphenyl-substituted cis-1,4-bis(triethylsiloxy)-2,5-cyclohexadiene-1,4-diyl (5fA), was synthesized on an ∼50 g scale by stereoselective cis-addition of 4-bromo-4'-lithiobiphenyl to 4-(4-bromophenyl)-4-hydroxy-2,5-cyclohexadien-1-one, which was synthesized on an ∼100 g scale. Platinum-mediated selective dimerization of the four-ring unit 5fB and subsequent reductive aromatization of the cyclohexadiene-diyl by H2SnCl4 gave 2 g of [8]CPP in 6.6% overall yield (10.2% on small scale).