A novel hydrate (SH2O) of nandrolone (NT) was prepared by anti-solvent methods. The crystallization processes with two schemes (A and B) were monitored by in-line near-infrared (NIR) spectroscopy. The amounts of SH2O in powder samples obtained by the anti-solvent crystallization and storage process were quantified by NIR combined with chemometrics methods. In-line NIR spectra from 4500 to 8000 cm-1 were chosen to capture physicochemical changes during the whole crystallization process. The combination of the principal component (PCA) results with offline characterization (scanning electron microscopy, powder x-ray diffraction, NIR) data showed that both schemes yielded high purity SH2O products, but the crystallization speed of Scheme B was significantly accelerated.