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Poly-(3-hydroxybutyrate), PHB, is a bacterial polyester in industrial demand as a biodegradable alternative to fossil-derived nondegradable plastics. Moreover, apart from being used directly as a bioplastic, valorization of PHB to its monomer building blocks and other value-added chemicals is feasible but less explored. In this study, Brønsted acid ionic liquid (BAIL) catalyzed depolymerization of PHB was investigated as a highly selective route to 3-hydroxybutyric acid, 3-HBA. The hydrolysis of PHB to 3-HBA was performed in a biphasic solvent medium composed of methyl isobutyl ketone (MIBK) and water, where the organic phase had dual roles as an efficient medium for dissolution of the polymer and as solvent for the monomeric products, which were enriched in this phase after cooling, with the Brønsted acid ionic liquid (BAIL) catalyst partitioned into the aqueous phase for facile recycling. The effects of reaction parameters, including the temperature, types of IL in terms of cations and anions, and the amount of water and IL, were studied to assess the yield of 3-HBA. Furthermore, protic acids such as sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid (p-TsOH) were also applied for comparison as acid catalysts for the hydrolysis of PHB to 3-HBA. Among the tested catalysts, the ILs containing the p-TsO- as anion as well as p-TsOH alone were found to be highly selective in promoting hydrolysis to 3-HBA, with complete depolymerization of PHB at >90% yield of 3-HBA in 4 h at 120 °C using a BAIL with sulfobutylated 1-methylimidazolium as the cation component and p-TsO- as the anion ([ImSO3H+][p-TsO-]). Although the use of p-TsOH as the sole catalyst also yielded efficient PHB hydrolysis with high reaction rates, it had a disturbing effect on the biphasic MIBK-water system by forming a single-phase reaction mixture at high 3-HBA yields, obstructing the recoveries of the products as well as the catalyst. In contrast, the biphasic reaction mixture remained intact when using IL as catalyst, which allowed facile and efficient separation of the product from the catalyst. Both the 3-HBA and the [ImSO3H+][p-TsO-] IL were recovered in high purity, the latter after applying a solvent extraction scheme based on ethyl acetate, whereby the recoveries of 3-HBA and IL reached ≈90%. The compositions of the synthesized ILs and the progress of the hydrolysis process, as well as the purity of the recovered product, were confirmed by NMR analysis. This sustainable approach to selective hydrolytic transformation of PHB into 3-HBA using a recoverable acidic IL catalyst in a biphasic solvent media of aqueous methyl isobutyl ketone hence resulted in efficient product separation and catalyst recovery.