This study used melt-electrospinning writing to fabricate three-dimensional fiber constructs by embedding them in a polyvinyl alcohol (PVA) matrix to obtain thin composite films. Fourier transform infrared spectroscopy (FTIR) and dynamic scanning calorimetry (DSC) were used to demonstrate an interaction between the polycaprolactone (PCL) fibrous phase and the PVA matrix phase. Following this, the mechanical deformation behavior of the composite was investigated, and the effect of reinforcement with three-dimensional fibrous constructs was illustrated. The specific strength of the composite was found to be five times higher than the specific strength of the neat PVA matrix. Additionally, the specific toughness of the composite was determined to be roughly four times higher than the specific toughness determined for the neat PVA matrix. These results demonstrate the potential of using melt-electrospinning writing for producing three-dimensional fibrous constructs for composite reinforcement purposes.