We report Nuclear Spectroscopic Telescope Array (NuSTAR) observations of NuSTAR J033202-2746.8, a heavily obscured, radio-loud quasar detected in the Extended Chandra Deep Field-South, the deepest layer of the NuSTAR extragalactic survey (∼400 ks, at its deepest). NuSTAR J033202-2746.8 is reliably detected by NuSTAR only at E > 8 keV and has a very flat spectral slope in the NuSTAR energy band (Γ = 0.55−0.64+0.62; 3-30 keV). Combining the NuSTAR data with extremely deep observations by Chandra and XMM-Newton (4 Ms and 3 Ms, respectively), we constrain the broad-band X-ray spectrum of NuSTAR J033202-2746.8, indicating that this source is a heavily obscured quasar (NH = 5.6+−0.80.9 × 1023 cm−2) with luminosity L10-40 keV ≈ 6.4 × 1044 erg s−1. Although existing optical and near-infrared (near-IR) data, as well as follow-up spectroscopy with the Keck and VLT telescopes, failed to provide a secure redshift identification for NuSTAR J033202-2746.8, we reliably constrain the redshift z = 2.00 ± 0.04 from the X-ray spectral features (primarily from the iron K edge). The NuSTAR spectrum shows a significant reflection component (R = 0.55+−0.370.44), which was not constrained by previous analyses of Chandra and XMM-Newton data alone. The measured reflection fraction is higher than the R∼0 typically observed in bright radio-loud quasars such as NuSTAR J033202-2746.8, which has L1.4 GHz≈1027 W Hz−1. Constraining the spectral shape of active galactic nuclei (AGNs), including bright quasars, is very important for understanding the AGN population, and can have a strong impact on the modeling of the X-ray background. Our results show the importance of NuSTAR in investigating the broad-band spectral properties of quasars out to high redshift.