Biomass requires trace metals (TM) for maintaining its growth and activity. This study aimed to determine the effect of TM supplementation and partitioning on the specific methanogenic activity (SMA), with a focus on cobalt and tungsten, during the start-up of two lab-scale Anaerobic Membrane Bioreactors (AnMBRs) treating saline phenolic wastewater. The TM partitioning revealed a strong accumulation of sodium in the biomass matrix and a wash-out of the majority of TM in the reactors, which led to an SMA decrease and a low COD removal of about 30%. The SMA exhibits a maximum at about 6 g Na⁺ L⁻¹ and nearly complete inhibition at 34 g Na⁺ L⁻¹. The dose of 0.5 mg L⁻¹ of tungsten increases the SMA by 17%, but no improvement was observed with the addition of cobalt. The results suggested that TM were not bioavailable at high salinity. Accordingly, an increased COD removal was achieved by doubling the supply of TM.