Relating to cyclotriphosphazene and its fluorescent nano-microsphere as well as a preparation method, the invention provides hexaminoacid ester phenoxyl cyclotriphosphazene, its fluorescent nano-microsphere and a preparation method thereof. Hexaminoacid ester phenoxyl cyclotriphosphazene has a general structural formula as shown in the picture, wherein, M is amino acid x ester. And hexaminoacid ester phenoxyl cyclotriphosphazene is prepared by first reacting 6 pairs of carboxyphenoxyl cyclotriphosphazene with thionyl chloride, and then adding amino-acid ester hydrochloride and an acid binding agent for reaction. Composed of hexaminoacid ester phenoxyl cyclotriphosphazene, the fluorescent nano-microsphere is prepared by the steps of: dissolving hexaminoacid ester phenoxyl cyclotriphosphazene in an organic solvent, then adding distilled water dropwisely, and pouring water, then conducting dialysis and freeze-drying, thus obtaining the fluorescent nano-microsphere. Hexaminoacid ester phenoxyl cyclotriphosphazene has stable structure, good biocompatibility, easy degradation, degradation product free of toxicity and inflammatory response, and its preparation method has a yield up to over 80%, mild reaction conditions, and a simple process, thus boasting very good industrial application prospects. Under ultraviolet excitation, the fluorescent nano-microsphere can generate a fluorescence phenomenon, and can serve as a carrier of targeting drug delivery.