Highly efficient removal of organic pollutants currently is a main worldwide concern in water treatment, and highly challenging. Here, vertically oriented mesoporous coatings (MCs) with tunable surface properties and pore sizes have been developed via the single‐micelle directing assembly strategy, which show good adsorption performances toward a wide range of organic pollutants. The micelle size and structure can be precisely regulated by oil molecules based on their n‐octanol/water partition coefficients (Log P) in the oil–water diphase assembly system, which are critical to the pore size and pore surface property of the MCs. The affinity and steric effects of the MCs can be on‐demand adjusted, as a result, the MCs show a ultrahigh adsorption capacity (263 mg g−1), surface occupancy ratio (≈41.92%), and adsorption rate (≈10.85 mg g−1 min−1) for microcystin‐LR, which is among the best performances up to date. The MCs also show an excellent universality to remove organic pollutants with different properties. Moreover, overcoming the challenges proposed by particulate absorbents, the MCs are stable and can be easily regenerated and reused without secondary contamination. This work paves a new route to the synthesis of high‐quality MCs for water purification.