In the last few decades, Pickering emulsions have regained attention due to the possibility of forming stable oil-in-water emulsions with interesting interfacial properties. As an example, the more and more stringent regulations on the products for home and personal care are pushing the market towards the use of biodegradable materials in order to reduce their environmental impact. In this scenario, an appealing opportunity is offered by the use of biodegradable polymeric nanoparticles (NPs) for the stabilization of fragrance oils in water. In this work, modular biodegradable NPs have been synthesized through a combination of ring opening polymerization and reversible addition-fragmentation chain transfer emulsion polymerization and used to produce limonene-in-water Pickering emulsions. This strategy allowed controlling independently the NP size, polymer molecular weight, and hydrophobicity acting on the microstructure of the constituting copolymers. Stable limonene-in-water Pickering emulsions could be obtained, with the size of the oil phase and the wetting by limonene that can be strictly controlled by tuning the NP physico-chemical properties. Finally, the adoption of thermo-responsive polymer chains within the shell of the Pickering emulsifiers enabled the on-demand destabilization of the emulsions and hence the selective dispensing of limonene by simply increasing the temperature.