In this study, the characteristic of hydrogen production and polycyclic aromatic hydrocarbons (PAHs) transformation during supercritical water gasification (SCWG) of coking sludge (400 °C - 450 °C, 1 min–30 min) were explored. The total gas yield was between 0.62 mol/kg OM and 1.05 mol/kg OM (on dry basis), and the proportion of CH4 and H2 was only between 5.41% and 6.44%. PAH content were increased from 194.92 mg/kg to 326.04 mg/kg, and mainly high molecular weight PAHs, which were formed from the Diels-Adler reaction of single aromatic hydrocarbon and the addition reaction of low molecular weight PAHs. High reaction temperature favored more active PAH formation than reaction time. The possible control methods for PAH formation during SCWG of coking sludge was proposed. H2O2 and KOH addition effectively reduce PAHs amount in solid residues by 46.67% and 38.33%, and KOH performed positive effect on hydrogen production. The work revealed that the inhibition of PAHs and hydrogen production were achieved from SCWG of coking sludge with KOH addition.