Functional microspheres with subtle designed molecular recognition sites is much highlighted in recent days. We here study the in situ molecular imprinting in the Stober synthesis of resorcinol-formaldehyde (RF) microspheres, and two different approaches are demonstrated. One approach is named as organic molecular imprinting, during which the target molecules of bisphenol A (BPA) are incorporated as the template in the gelation of RF resin. The other is named as inorganic molecular imprinting, during which the template is introduced together with inorganic precursor of titanate. The sizes of the produced spheric particles are found to rely on the ratio of ethanol/water in the reaction medium. Recognition sites which are BPA specific have been detected on both the RF and RF-carbon/TiO2 spheres, and the latter show slightly higher capacity and selectivity in rebinding tests. Importantly, the integration of the photo active nano TiO2 on the submicron spheric carbon support with BPA imprinted sites is of unique advantages, which exhibits as the specific high photocatalytic efficiency on BPA degradation under UV light. This, together with the high selectivity, substantial efficiency and operable uniform size of the composite spheres would be useful in the engineering for environmental and analysis fields.