Sensor development has been reliant on planar Au and Ag nanoparticle research. The current findings explored a unique 3-D network of crystalline TiO2 nanoparticles linked as nanofibers. In addition to the favorability of using TiO2 for chemical and bio-molecular sensing, the nanofiber network provides molecular diffusion control and an increased confocal volume signal. Controlled femtosecond laser synthesis is also demonstrated that directly impacts surface-enhanced Raman spectroscopy detection of two common environmentally harmful chemicals: bisphenol A and diclofenac sodium salt. These findings assert that 3-D nanofibrous network porosity optimization is crucial for Raman monitoring of drinking water.