Integrated analytical approaches can be used to determine the trace concentrations of analytes in water matrices. Here we designed and compared two novel and facile, integrated polysaccharide adsorbent SPE-Self assembled MEPS (solid phase extraction and self-assembled microextraction by packed sorbent) protocols based on chitin, and cellulose acetate respectively, for simultaneously determining the ultralow concentrations of three mononitrophenols (MNPs) in water. In addition, we reported computational, and empirical, interaction profiling, for providing insights into the possible interactions among chitin-MNP, and cellulose acetate-MNP, respectively. The integrated SPE-MEPS analytical platform enhances the MNPs detection limits, scalability and recoveries from individual water matrices with the additional ease of use. Aside from offering improved control over lower scalability range (0.05–5 ng/mL) with both adsorbents Chitin and CA as compared to previous analogues reported methods, limits of detection (LODs) were as low as 0.01–0.03 ng/mL with Chitin and 0.008–0.025 ng/mL with CA, in quality control samples. By integrating SPE with MEPS, and chromatographic separations with high performance liquid chromatography-ultra violet detector (HPLC-UV), we were able to determine three MNPs at ppt (pg/mL) levels in different water matrices. This approach may find diverse applications in water monitoring at trace levels. Finally, and most importantly, to the best of authors knowledge, this study marks the first time that integrated SPE-MEPS analytical platform has been used for the efficient trace analysis in analytical chemistry. © 2019 Elsevier B.V.