Polymeric metal coagulants are increasingly being used to improve coagulation efficiency, yet the research on the development of titanium and particularly polytitanium salts remains limited. This study is the first attempt in the synthesis, characterization, and application of polytitanium salts as coagulants. Polytitanium tetrachloride (PTC) solutions with different basicity values B (OH/Ti molar ratio) were prepared using a slow alkaline titration method. Jar tests were conducted to assess coagulation performance using both synthetic and real raw water samples, and the floc characteristics were monitored online using a laser diffraction particle size analyzer. Electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) was utilized to identify various Ti species, with the results providing strong evidence of the presence of various hydrolyzed Ti species in the titanium aqueous phase. Compared to titanium tetrachloride (TiCl4), higher or comparable turbidity and organic matter removal efficiency could be achieved by PTC with improved floc characteristics in terms of size, growth rate, and structure. Besides, the water pH after PTC coagulation was significantly improved toward neutral pH. This study indicates that PTC is an effective and promising coagulant for water purification. Besides, the PTC flocculated sludge was able to recycle and produce functional TiO2 photocatalyst.