The Gulf of Trieste (Northern Adriatic Sea, Italy) is the coastal area of the Mediterranean Sea most highly contaminated by mercury (Hg) due to fluvial inputs from the Isonzo/Soča River system, draining over 500 years’ worth of cinnabar extraction activity from the Idrija mining district (Western Slovenia). The aim of this research is to investigate the concentration of Hg in hair samples taken from the general population of the Friuli Venezia Giulia (FVG) Region coastal area, as a marker of chronic exposure to Hg. Three hundred and one individuals — 119 males and 182 females — were recruited by convenience sampling in Trieste in September 2021. An amount of approximately 100 mg of hair was collected from the occipital scalp of each participant to measure the respective Hg concentrations (expressed as mg/kg). Moreover, participants completed a self-report questionnaire collecting extensive socio-demographic and life-style information. A multiple linear regression analysis was employed to investigate factors associated with increased levels of Hg concentration in hair. A mean Hg concentration in hair of 1.63 mg/kg was found, slightly above the 1.0 mg/kg threshold recommended by the WHO for pregnant women and children, although still well below the no observed adverse effects level (NOAEL) of 10 mg/kg. Among respondents, 55.6% showed a Hg concentration in hair > 1 mg/kg, 22.9% > 2 mg/kg, and 2 participants exhibited Hg levels > 10 mg/kg. The adjusted mean hair Hg level increased in those subjects who reported a preference for shellfish/crayfish/mollusks (RC = 0.35; 95%CI: 0.16; 0.55), whereas it decreased in those who reported a preference for frozen fish (RC = -0.23; 95%CI: − 0.39; − 0.06). Though a risk alert for Hg exposure for coastal residents from FVG is deemed unnecessary at this time, it is recommended that pregnant women limit their ingestion of locally caught fish to < 4 servings/month.