In this study, metallurgical-slag-based binder (MSB) with different dosages of calcium hydroxide (CH) was mixed with high-arsenic-containing mine tailings (HAMT) to form green mining fill samples (GMFs) for As solidification/stabilisation (S/S). The As leaching characteristics of the GMFs were evaluated using pH-dependent leaching tests, semi-dynamic leaching tests and toxicity leaching tests. The effective diffusion coefficient (De) decreased from 6.98 × 10−14 to 5.90 × 10−15 cm2/s and the leachability index (LI) increased from 13.53 to 14.73 after 3 wt.% CH was added to the GMFs. The GMFs containing 0 wt.% CH (GMF-0C) and those containing 3 wt.% CH (GMF-3C) reached pH = 2 with acid addition amounts of 9.0 meq/g-dry and 9.3 meq/g-dry at 90 d curing time, and the maximum As leaching concentrations of GMF-0C and GMF-3C reached 10.47 mg/L and 7.47 mg/L, respectively, indicating that GMF-3C exhibited better acid neutralisation and As retention capacities than GMF-0C. Further, a Tescan Integrated Mineral Analyser (TIMA) was used to analyse the dominant hydration products of GMF-3C, which revealed that calcium silicate hydrate, CASH, ettringite and zeolite phases represented approximately 22.5 wt.% of the products. These results provide an understanding regarding the safe large-scale utilisation of GMFs.