Cigarette mainstream smoke (MSS) is a complex aerosol consisting of a vapour and a particulate phase. Cigarette design has been largely evolved over the last decades with the incorporation of new tobacco processes, papers, filters, and several ingredients (flavorings, casing materials, humectants), which either alone or in combination have the potential to modify the quantity and/or the quality of the smoke yielded. In the present study, polycyclic aromatic hydrocarbons (PAHs), n-alkanes and branched alkanes were determined in the particulate and gas phase of the MSS yielded from 59 manufactured cigarette brands (brands of unknown tobacco and blend type commercially available in the Greek market) with variable tar yields and physical/ technological characteristics (existence/absence of filtered tip, tar yield, cigarette length, cigarette diameter, ventilation rate, pressure drop). The potential associations of particulate- and gas-phase organic components with cigarette technology and other MSS components (e.g. TPM, tar yield, nicotine and CO) were investigated. The data set offers a unique perspective into the assessment of smokers' exposure to hazardous constituents of cigarette smoke.