Cellulose acetate (CA) mats modified with poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (PEO-b-PPO-b-PEO or EPE) and sol–gel synthesised titanium oxide (TiO2) nanoparticles were successfully fabricated by using electrospinning technique. Under the same preparation conditions, higher spinnability was achieved for EPE triblock copolymers modified mats. All fabricated mats showed a micrometric multilayer structure, which enabled layer-by-layer peeling. The addition of TiO2 nanoparticles facilitated the peeling process. The diameter of the fibres was ~ 3 times lower after the incorporation of sol–gel synthesised TiO2 nanoparticles. TEM images confirmed that under electrospinning conditions the PPO block domains were able to microphase separated from the PEO block/CA phase. Additionally, the introduction of sol–gel synthesised TiO2 nanoparticles led to an inorganic network formation with nanoparticle size equal to ~ 8 nm in diameter. Moreover, the addition of TiO2 nanoparticles increased the hydrophobicity of the mats and their self-cleaning ability, being more effective for TiO2/CA than for TiO2-EPE/CA due to the partial absorption of water by EPE triblock copolymer. Young’s modulus of fabricated mats improved drastically with the addition of TiO2 nanoparticles, as well as their physical integrity in polar and nonpolar solvents. Fabricated mats with enhanced spinnability, which maintain CA mat features as well as the properties associated with sol–gel synthesised TiO2 nanoparticles, can find a wide range of applications.