High-resolution spectroscopy (R>100,000) is a robust and powerful tool for directly characterizing exoplanet atmospheres that is applicable to both transiting and non-transiting planets, as well as those with relatively large projected separation angles. In the infrared, the technique has unambiguously revealed the presence of complex molecules, such as water, in hot Jupiters, as well as measuring exoplanet rotation rates and their day-to-night winds. In the optical, the technique is highly suited to characterizing the atmosphere of our nearest rocky neighbor, Proxima b, by detecting the Doppler shift and modulation of its host star spectrum as reflected by the planet’s dayside. However, the technique is currently not yet robustly proven at optical wavelengths. Here, we present new results on the non-transiting hot Jupiter, 51 Peg b, using 5 half nights of optical HARPS-N spectroscopy from the 3.5m TNG telescopes. We aimed to detect reflected light from the planet’s dayside and obtain one of the most detailed exoplanet reflection spectra to date, spanning 387-691 nm in bins of 50nm. Our goal is to strongly constrain previous claims of a very high albedo or highly inflated radius for 51 Peg b and assess the potentially cloudy nature of the planet. This will also guide us in using high-resolution spectroscopy to characterize Proxima b in the era of the extremely large telescopes.This work was performed in part under contract with the California Institute of Technology/Jet Propulsion Laboratory funded by NASA through the Sagan Fellowship Program executed by the NASA Exoplanet Science Institute.