Capturing and recovering naphthalene as a profitable chemical from hot flue gas are of significance in terms of environmental protection with economic benefits, for which the adsorption technology using high-performance sorbents provides the key step for success in practical applications. Carbonaceous materials with hydrophobic natures have been shown to render high affinities with non-polar naphthalene, but remain challenging due to difficulties in tackling the trade-off between adsorption and desorption. This work reports a systematic investigation with deeper insights into adsorption equilibria, kinetics and regenerabilities of gaseous naphthalene on typical carbonaceous sorbents originated from different texture properties, including ordered mesoporous carbons (CMK-3, CMK-5 and FDU-15), carbon nanotubes (SWCNT and MWCNT) and a coconut-shell-based activated carbon (AC). The adsorption isotherm and breakthrough curves at wide feed concentration ranges and temperature programmed desorption curves for each sorbent were obtained along with series of theoretical model fitting. FDU-15 and CMK-5 were demonstrated as superior sorbents with high maximum adsorption capacities (1.13 and 1.735 mmol/g) and low desorption activation energy (62.66 and 72.68 kJ/mol), respectively exhibiting advantages of the 3-dimensional diffusion-controlled desorption upon a hexagonal pore arrangement and the efficient adsorption upon a reasonable mesopore-micropore hierarchical structure, in contrast to poor kinetics on pure microporosity (AC) and 1-dimensional topologies (CNTs). Deeper insights into the morphology-affinity relationship revealed advantageous naphthalene transport behaviors over 3-dimensional ordered mesoporosities with appropriate coexisting microporosities and narrower primary size (2–5 nm) or diverse forms of mesopore, which contribute toward reaching comprehensive balances of sorption performances.