•Rejection of ten PhACs by ceramic fine ultrafiltration membranes was studied.•Effect of feed solution pH on the removal of PhACs was analysed.•Results demonstrated that rejection of anionic PhACs was strongly pH-dependent.•The formed foulant layer on the membrane acted as a secondary membrane. This study investigates the influence of feed solution pH and fouling on the rejection of ten selected pharmaceutically active compounds (PhACs) with different physicochemical characteristics (molecular weight, water solubility, log KOW, pKa, dipole moment, etc.) by three multichannel ceramic ultrafiltration membranes, ranging from 1 to 8kDa, in order to improve their removal from water. For this purpose, the comparison between filtration of PhACs in deionised water (Feed I) and in real wastewater effluent (Feed II) was performed, demonstrating that the variation of pH and the formation of a foulant layer altered the separation mechanism and hence the rejection values of each PhAC varied. Higher rejections of most of the PhACs were higher at slightly alkaline pH, especially for anionic compounds in the filtration with real wastewater. In these conditions, flux decline was more severe. The formed fouling layer onto the hydrophilic membrane surface acted as a secondary barrier for separation with different properties like hydrophobicity and charge. Electrostatic interactions were the main separation mechanism in the filtration of PhACs in deionised water, while the hydrophobic/hydrophilic interactions played a crucial role in the filtration experiments with real wastewater effluent. Thus, the reported results indicated that the rejection of pharmaceutically active compounds was strongly pH-dependent, except for hydrophilic neutral compounds (acetaminophen and caffeine), which showed a pH-independent behaviour with low rejection values.