The study was aimed at the reutilization of oyster shells (OS) as a calcium-based additive to turn sewage sludge ash into phosphate fertilizer, employing the oxygen-enriched combustion technology. This process transformed all non-apatite inorganic phosphorus into apatite phosphorus with the incorporation of a 7.5% Ca-based additive. OS demonstrated comparable effectiveness to CaO in catalyzing this transformation in the oxygen-steam atmosphere. The amount of OS added and the atmosphere type significantly influenced the P bioavailability of sewage sludge ash. The oxygen-steam atmosphere, with its increased water vapor concentration, facilitated the decomposition of CaCO3 and initiated reactions with calcium phosphate to form hydroxyapatite, thus substantially enhancing P bioavailability. The oxygen-steam atmosphere increased not only metal volatilization but also the ecological toxicity of residual metals, particularly Pb, mainly in the form of F2. Excessive OS addition appeared to elevate the toxicity of Cr. Therefore, additional strategies for metal removal or passivation are needed to improve the safety of sewage sludge ash with high metal content.