Chitosan and pectin are abundantly found biopolymers in nature that are derived from renewable resources. On the other hand, the chemical structure of these biopolymers creates problems during the production of their nanofibrous films by the electrospinning technique. In this study, the electrospinning of the chitosan/pectin blend system was facilitated using natural, starch-derived cyclodextrin (hydroxypropyl-γ-cyclodextrin (HPγCD)) molecules and nanofibrous films were generated with a green approach in which there was no use of a carrier polymer or toxic solvent. The nanofibrous films obtained with different chitosan/pectin ratios showed high swelling (water uptake) property (∼1340 to 1510%), which suggested the hydrogel-forming capacity of these electrospun films. Here, the HPγCD molecules were further utilized and curcumin, a well-known bioactive compound, was encapsulated into HPγCD cavities by inclusion complexation. This time, HPγCD–curcumin inclusion complexes (ICs) were mixed with chitosan/pectin blends using the predetermined ratios, and freestanding nanofibrous films were successfully produced having an ∼89% curcumin loading efficiency. The ultimate nanofibrous films demonstrated a pH-responsive release profile of curcumin in pH 5.4 and 7.4 media besides their high swelling feature. Briefly, chitosan/pectin/CD-IC nanofibrous films can be a promising alternative to biomaterials produced with synthetic sources by holding the unique properties of biopolymers, CD, and nanofibers.