Crystalline pure NaTi2(PO4)(3) (NTP) powder was synthesized at 700 degrees C using a simple and low energy, hybrid inorganic-organic, steric entrapment method. Sodium nitrite (NaNO2) and ammonium phosphate dibasic ((NH4)(2)HPO4) dissolved in water, whereas titanium (IV) isopropoxide (Ti[OCH(CH3)(2)](4)) hydrolyzed in water. Ethylene glycol (HOCH2CH2OH) was used as a polymeric entrapper and hydrolysis of the Ti source was hindered by its dissolution in isopropyl alcohol. The resulting NTP powder was characterized by thermogravimetric analysis/differential thermal analysis, X-ray diffractometry, scanning electron microscopy, specific surface area by Brunauer-Emmett-Teller nitrogen absorption, and particle size analysis. Furthermore, C, H, N were measured by the classical Pregl-Dumas method. The thermal expansion behavior in all {hkl} pole directions was also determined by in situ high-temperature X-ray diffraction using synchrotron radiation and was found to be in agreement with other published studies.