It was discovered by Johann Palisa October 15, 1891 in Vienna. He named the asteroid for his daughter, Florentina.<ref>Meanings of asteroid names (1-500)#301</ref> Between 1874 and 1923, Palisa discovered a total of 122 asteroids.
A group of astronomers, including Lucy d'Escoffier Crespo da Silva, contributed data toward the discovery of spin-vector alignments in the Koronis family, which includes (321) Florentina. This was based on observations made between 1998 through 2000. The collaborative work resulted in the creation of 61 new individual rotation lightcurves to augment previous published observations.<ref>Slivan, S. M., Binzel, R. P., Crespo da Silva, L. D., Kaasalainen, M., Lyndaker, M. M., Krco, M.: “Spin vectors in the Koronis family: comprehensive results from two independent analyses of 213 rotation lightcurves,”Icarus, 162, 2003, pp. 285-307.</ref>
(321) Florentina sections
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