We describe the inorganic polymer K4P8Te4 which is soluble, giving solutions that exhibit white emission upon 355 nm laser irradiation. An indirect band gap semiconductor (E-g approximate to 1.4 eV), K4P8Te4 crystallizes in the space group P2(1)/m, with a = 6.946(1) angstrom, b = 6,555(1) angstrom, c = 9.955(2) angstrom, and beta = 90.420(3)degrees at 173(2) K. The compound features infinite chains of [P8Te44-] with covalent P-Te bonding and exhibits reversible crystal-glass phase-change behavior. When deposited from solution, the material forms highly crystalline K4P8Te4 nanospheres. The thermal analysis, FT-IR, UV-vis diffuse reflectance, P-31 magic angle spinning solid-state NMR spectroscopy, and pair distribution function (PDF) analysis for the crystal and glass forms and ab initio electronic structure calculations by the. screened-exchange local density function approximation are also reported. Speciation of K4P8Te4 in solution studied with P-31 solution-state NMR spectroscopy, electrospray ionization mass spectrometry, and PDF analysis indicate exfoliation of [P8Te44-] chains followed by rearrangement into molecular species.