High internal phase emulsion (HIPE) technology has been emerged as a prodigious source to create tailor-made porous structures. This type of emulsion contains significantly higher amount of water in it, which is only possible with special type of stabilizers. Most specifically, the monomers with sufficiently high solubility in water such as methyl methacrylate (MMA) make it more cumbersome to stabilize in the form of HIPE. Here we have reported the combination of stabilizers including fluorinated block copolymer Poly (2-dimethylamino)ethyl methacrylate-b-Poly(trifluoroethyl methacrylate) (PDMAEMA-b-PTFEMA) and humic acid modified iron-oxide (HA-Fe3O4) nanoparticles (NPs) to stabilize HIPE, which resulted in highly porous and interconnected products. Fluorinated block copolymers with inherent hydrophobic nature along with iron oxide nanoparticles increased the water repellency of MMA based polymeric monoliths. Increasing the amount of stabilizer increased the porosity and BET specific surface area to 83.8% and 27 ± 0.8 μm, respectively. The prepared porous materials demonstrated hydrophobic characteristics while adsorbing oil from the surface of water up to 16 g/g. Moreover, the adsorbed oil from the prepared monolith was recovered by using simple centrifugation method without damaging the structure. This research opens new avenues to prepare more useful oil and water separation materials such as membranes, pollutant adsorbers, and so on.