The interfacial interaction of carbon nanotubes (CNTs) significantly enhances the output capability of piezoelectric nanogenerators (PENGs). However, overcoming the limitation of low specific surface area in one-dimensional materials remains a significant challenge. This paper introduces a hydrothermal method for composite MOF (C-M) using CNTs and MOF-5, demonstrating localized co-doping between them. Coaxial electrospun piezoelectric fiber membranes (C-MNF) were then prepared using PVDF/PAN as the matrix. Benefiting from C-M's excellent crystallinity and its synergistic interaction with the polymer matrix, the C-MNF-based PENG showed a 125 % increase in output voltage, reaching ∼25 V, compared to coaxial membranes simply mixing MOF-5 and CNTs. As a result, its short-circuit current was ∼1.8 μA, with a piezoelectric coefficient d 33 of ∼400 pC N -1 . Consequently, this material exhibits superior piezoelectric output capabilities, paving the way for future functional material fabrication.