The reactions of octachlorocyclotetraphosphazene, N(4)P(4)Cl(8), with N(2)O(2) donor-type aminopodands (1a, 1b, 1g, and 1h) afforded two kinds of derivatives, namely, spiro-ansa-spiro (sas) (2a, 2b, 2g, and 2h) and ansa-spiro-ansa (asa) (3a and 3b) phosphazenes. The partly substituted sas phosphazenes (2a and 2b) reacted with excess pyrrolidine and morpholine in tetrahydrofuran to produce the tetrapyrrolidino (2c and 2d) and morpholino (2e and 2f) derivatives. The reactions of the asa phosphazenes (3a and 3b) with excess pyrrolidine and morpholine produced gem-2-trans-6-dichloropyrrolidinophosphazenes (3c and 3d) and -morpholinophosphazenes (3e and 3f). However, the fully substituted products were not obtained in these solvents. In addition, the expected fully substituted compound was not obtained from the reaction of 3a with excess pyrrolidine by standard or microwave-assisted methods. The reaction of the long-chain starting compound (1g) with N(4)P(4)Cl(8) gave sas (2g) and the interesting 2,6-ansa-spiro-bicyclo product (bicyclo-2,6-as; 4g), while the reaction of 1h with N(4)P(4)Cl(8) yielded only sas (2h). The structural investigations of the compounds were verified by elemental analyses, mass spectrometry, Fourier transform infrared, and DEPT, HSQC, HMBC, (1)H, (13)C, and (31)P NMR techniques. The crystal structures of 2b, 3a, 3b, 3e, and 4g were determined by X-ray crystallography. Compounds 2a-2h, 3a-3f, and 4g had two stereogenic P atoms. Compound 3b had one enantiomer according to the Flack parameter, and 3f was a racemic mixture, as shown by chiral high-performance liquid chromatography and chiral-solvating-agent, (R)-(+)-2,2,2-trifluoro-1-(9'-anthryl)ethanol, experiments. Furthermore, compounds 2a, 2c, and 2d exhibited weak antibacterial activity against (G+) bacterium, and 3c and 3d displayed moderate antifungal activity against Candida tropicalis. Gel electrophoresis data demonstrated that 2e, 3c, and 3e promoted the formation of DNA cleavage. The prevention of BamHI digestion by 2a-2f and 3a-3f, except 2b and 2e, disclosed binding with GG nucleotides in DNA.