This invention relates to water-soluble complexes of optical brighteners with quaternary ammonium compounds which are substantially free from unwanted salts. Such complexes are formed through ionic bonds formed between the two compounds. The inventive complexes are then removed of substantially all excess unwanted salt so as to obtain an optical brightener compound which easily solubilizes within, dispenses from, and exhibits excellent compatibility with standard detergent and softener compositions, which exhibits the desired degree of affinity for various substrate surfaces, including textile, paper, wood, and plastics, as well as within leak detector formulations, and which provides a desired accumulation effect on substrate surfaces upon repeated treatments. Such inventive complexes can also be utilized to whiten thermoplastics and thermosets. Furthermore, this invention also concerns methods of making and utilizing such inventive optical brightening complexes.