The invention provides a 99mTc marked multivalence sugar fan-shaped dendrimer complex with the formula being 99mTc(R-HYNIC)(Tricine)m(L)n and further provides application of the complex, a multivalence sugar fan-shaped dendrimer ligand for preparing the complex and a preparation method thereof. The multivalence sugar fan-shaped dendrimer ligand can form the 99mTc marked complex with a co-ligand, a selectable coligand and radioactive pertechnetate, the complex is high in radiation chemical purity, good in stability and biological performance, high in specific activity, high in liver uptake value and target-to-non-target ratio, capable of being used as a hepatic cell asialoglycoprotein receptor SPECT photographic developer, easy and convenient to prepare and low in cost and has the large-scale and wide-application value.