Titania plays a very important role in phosphoproteome and bioanalysis due to its extreme robustness, excellent chemical stability in acid and basic media and unique chemo-affinity for organic phosphates. In this review, the recent developments and important applications of titaniabased stationary phase in phosphoproteome and bioanalysis including sample pretreatment and enrichment for high performance liquid chromatography (HPLC) have been discussed. We highlight the application of titania-based stationary phase in the separation of phosphopeptides, nucleotides, phospholipids, sugar phosphates, drugs and herbicides. The future perspectives of titania-based stationary phase are finally addressed.