A novel luminescent hybrid inorganic–organic molecular assembly was synthesised by the condensation of hexakis cyclotriphosphazene hydrazide (CTP-Hyd) with six units of 10-octyl-10H-phenothiazine-3-carbaldehyde (R-PTZ-CHO) for the first time. In particular, synthesis of a new precursor, an inorganic heterocycle, CTP-Hyd, has been developed to append PTZ units on the periphery of the thermally stable CTP ring via condensation. The luminescent hybrid material prepared by the convergent approach was well characterized at each step using a plethora of techniques like FT-IR and multi-nuclear NMR including ¹H, ¹³C and ³¹P as well as HRMS/MALDI-TOF data. Further, the photophysical properties of the synthesised hybrid material were investigated by UV-visible absorption, steady state and time resolved photoluminescence spectroscopy. The synthesised hybrid molecule shows extraordinary solvent compatibility and shows tunable emission in the yellow–green region. A relatively large Stokes shift of 82 nm was observed with varying solvent polarity owing to the charge transfer nature of the electronic transition in the hybrid molecule. The thermal stability and electrochemical properties of key substrates and products were studied using thermal gravimetric analysis (TGA) and cyclic voltammetry studies respectively. The high T_d value of 326 °C inferred that the hybrid CTP-PTZ exhibited superior thermal stability. This study shows important insight into the understanding of the hybrid material properties for possible application in the areas of optoelectronics and bio-imaging.