The [n]cyclo-meta-phenylenes ([n]CMP) are macrocyclic molecules consisting of benzene rings linked at the meta positions. Even though the first syntheses of [n]CMP was reported by Staab in 1964, and the utility of the framework structures was further emphasized via CMP-based spherand hosts by Cram, there has generally been little attention paid to these interesting macrocycles. Recently, through the introduction of [n]cyclo-2,7-naphthylenes ([n]CNAP), we disclosed that macrocyclic aromatic hydrocarbons possess intrinsic thermal stabilities and bipolar charge carrier transport abilities in organic light-emitting diode (OLED) devices. Based on the result, we envisioned that [n]CMP would thus constitute potential candidates for material applications. Here we report a concise one-pot synthesis of [n]CMP using a nickel-mediated coupling reaction. The scalable synthesis of [n]CMP allowed us to explore their application for OLED, revealing high external quantum efficiencies (EQE) of [n]CMP-based devices. [n]CMP was prepared in gram-scale via a nickel-mediated Yamamoto-type coupling. A solution of 20 g of m-dibromobenzene was heated in the presence of Ni(cod)2/2,2’-bipyridine (cod = 1,5-cyclooctadiene) at 80 ºC for 1 h in toluene and N,N’-dimethylformamide, affording a mixture of [n]CMP with n = 5–14. After the purification, [5]-, [6]-, [7]-, [8]- and [9]CMP were isolated in 17% (1.10 g), 10% (667 mg), 7% (504 mg), 1% (73.1 mg), 1% yield (65.8 mg), respectively. The structures were clearly determined by X-ray crystallographic analysis, and the Hirshfeld surface analysis of the structures exhibited that the ubiquitous C–H•••π intermolecular contacts predominated in the crystals. Examination of physical properties of the macrocycles showed favorable characteristics for the device application: transparency in visible-light region and high thermal robustness of the macrocycles guaranteed the fabrication of optoelectronic devices via sublimation process. We indeed employed [5]- and [6]CMP as hole transport layers (HTL) and electron transport layers (ETL) in OLED devices through sublimation. As a result, the devices of CMP in ETL showed relatively low EQE, but high performance of 13.9% and 13.2% of EQE was recorded on the devices of [5]- and [6]CMP in HTL, respectively, demonstrating the utility of [n]CMP scaffolds for the material application.