Three novel polyphosphazene-functionalized diaminobutane poly(propyleneimine) dendrimers have been prepared and investigated for their properties as prospective hydrophobic drug delivery systems. The solubilization and release properties of these functionalized dendrimers have been investigated by absorption and fluorescence spectroscopy by using pyrene as a probe. The introduction of amphiphilic phosphazene groups at the external surface of the dendrimers affects the solubilization and guest release properties compared to the behavior of the parent dendrimers. The release of encapsulated guest molecules is triggered by the addition of sodium chloride solution. It has been established that these novel dendrimeric compounds exhibit useful protective and targeting properties. These properties render the new molecules promising candidates for salt-responsive controlled-release systems, possibly including prospective drug delivery applications.