The preparation of three different functionalized palladium nanoparticles (PdNPs) systems for room temperature BTX (benzene, toluene, p‐xylene) sensing detection and their morphostructural characterization is described. PdNPs are prepared through a two‐phase water/toluene wet chemical reduction method in the presence of bifunctional organic thiols as stabilizing agents suitable for the formation of covalently linked PdNPs networks: p‐terphenyl‐4,4″‐dithiol (PdNPs‐TR), biphenyl‐4,4′‐dithiol (PdNPs‐BP), or with 9,9‐didodecyl‐2,7‐bis(acetylthio)fluorene (PdNPs‐FL). Comparing the hydrodynamic diameter values, TR and BP ligands help to obtain networks consisting of spherical NPs of about 2 nm, in which each bifunctional ligand act as a bridge between PdNPs. In contrast, PdNPs‐FL show a population centered at <2RH> = 45 ± 5 nm. To perform preliminary gas sensing measurements, PdNPs networks are cast deposited on interdigitated electrodes to study their resistive response toward volatile organic compounds (VOCs) such as benzene (0–5%), toluene (0–1.7%), and p‐xylene (0–0.4%) (BTX) and common interfering gases (H2S, NH3, SO2, and relative humidity, RH). PdNPs‐FL show enhanced response to BTX with an appreciable response also toward H2S and RH. PdNPs‐TR exhibit a better ability to discriminate benzene gas with a negligible response after H2S exposure. Moreover, all the PdNPs systems show little to no response to NH3 and SO2 gases, offering an interesting perspective in practical sensing applications. [ABSTRACT FROM AUTHOR]