Three kinds of bis(aromatic fluoride) compounds, 3,5-bis(4-fluorobenzoyl)biphenyl (1), 3,5-bis(4-fluorobenzoyl)-1,1′:4′,1″-terphenyl (2), and 3,5-bis(4-fluorobenzoyl)-1,1′:4′,1″:4″,1′′′-quaterphenyl (3), were synthesized by cross-coupling of the corresponding triflates with phenylboronic acid. Linear poly(ether ketone)s (1x, 2x, and 3x) having phenyl, biphenyl, and terphenyl side groups, respectively, were prepared by the polycondensation of the bis(aromatic fluoride) compounds with bisphenol A (a) and 4,4′-dihydroxybiphenyl (b) in N-methyl-2-pyrrolidone. The obtained poly(ether ketone)s were characterized by X-ray diffraction, differential scanning calorimetry, and thermogravimetry. The structure–property relationships of these poly(ether ketone)s were examined and compared with those of poly(ether ketone)s (4x) having no side group, which were prepared from 3,5-bis(4-fluorobenzoyl)benzene (4). The properties of the poly(ether ketone)s, solubilities, and thermal properties were compared and discussed based on the length of the side groups.