Electrospinning and electrospraying nanotechnologies were used to valorise agro-industrial residues into biohybrid controlled-release polyphenol (CRP) scaffolds. Four polyhydroxybutyrate ± polycaprolactone (PHB±PCL) architectures were fabricated that differed in polymer phase, Klason lignin from hazelnut-shell (HS-KL) presence vs absence and co-location with grape-pomace polyphenols (GP-PP), as well as distribution between fibres and bead-like depots. Scaffolds were characterised using optical microscopy/stereomicroscopy/SEM, FTIR, UV/VIS spectroscopy and dynamic water contact angle (absorption). GP-PP release was monitored for 14 days at ~25 °C and 37 °C, the latter representing shallow-soil hot-spell conditions in Mediterranean zones. All matrices exhibited multimodal release, with modest initial bursts and three phases (burst, mid, and late tail), analogous to controlled-release fertiliser profiles. At ~25 °C, the PHB/PCL matrix with HS-KL confined to PHB fibres and GP-PP in large PCL beads showed the highest total GP-PP release, whereas the architecture with HS-KL and GP-PP co-located in both PHB and PCL fibres and in PCL depots combined high total release with a smoother, well-metered late phase. At 37 °C, this HS-KL-GP-PP co-located scaffold was the most robust, retaining the highest total and late tail release. These results identify HS-KL-GP-PP co-located PHB/PCL architectures as promising carriers for temperature-resilient delivery of bioactive polyphenols in Mediterranean agrosystems.