We have fabricated nanofiber mats as sorbent materials for passive sampling devices for monitoring organic pollutants in water and sediment. Equilibrium partition coefficients with 4 log units were achieved for most hydrophobic and hydrophilic pollutants with our mats. To model sorption, a strong linear free energy-quantitative structure activity relationship was developed. To increase monitoring scope and improve capture ability for targeted pollutants, we optimized nanofiber mats by introducing chemical composites and functionalizing polymer structure.