The search for new biomaterials intended for biomedical applications has considerably intensified in recent years. Herein, the synthesis and characterization of a new aliphatic biodegradable copolyester named PBS/PBDL (poly(butylene succinate-co-butylene dilinoleate)) is reported. Surfactant-free, narrowly distributed, nanosized spherical particles (R_H < 60 nm) have been produced from the biodegradable material by applying a single-step nanoprecipitation protocol. Their structure was characterized in detail by employing a variety of scattering techniques and transmission electron microscopy (TEM). Combined SLS and DLS measurements suggested that the nanoparticles comprise a porous core conferring a non-compact characteristic. Their porosity enables water to be entrapped which is responsible for their pronounced stability and relatively fast degradation as followed by size exclusion chromatography (SEC). The polymeric nanoparticles could be loaded with the hydrophobic model drug paclitaxel (PTX) with an encapsulation efficiency of ∼95% and drug loading content of ∼6–7% w_drug/w_polymer. The drug release was followed by HPLC and scattering measurements (DLS, SLS and SAXS). The drug encapsulation and release modifies the inner structure of the nanoparticles, which holds a large amount of entrapped water in the drug-free condition. PTX encapsulation leads to replacement of the entrapped water by the hydrophobic model drug and to shrinking of the nanoparticles, probably due to favorable drug–polymer hydrophobic interactions. Cell viability experiments demonstrated that the nanoparticles are biocompatible and non-toxic, making them potentially useful for applications in nanomedicine.