The hydrophilicity of bis(3-allyl-3,4-dihydro-2H-1,3-benzoxazinyl)isopropane(B-ala) polybenzoxazine film and superhydrophobic polybenzoxazine-hybrid surface can be controlled through UV exposure to change the ratio of intra- to intermolecular hydrogen bonds. A fraction of the intramolecular hydrogen bonding of the as-cured sample will convert into intermolecular hydrogen bonding upon UV exposure and thus results in an increase of hydrophilicity. This simple method allows for manipulating the hydrophilicity at selected regions on a superhydrophobic polybenzoxazine hybrid surface to create a patterned surface with superhydrophobic and superhydrophilic regions. Additionally, we have found that the superhydrophobic polybenzoxazine-silica hybrid surface exhibits good adhesion of water droplets after UV exposure, which can be served as a "mechanical hand" to transfer water droplets from a superhydrophobic surface to a hydrophilic one.