The correlation between specific meteorites and asteroids is a long-standing problem. The best-known correlation seems to be the HED–Vesta, although several problems still remain to be solved. We report the spectral reflectance analysis (0.4–2.5 μm) of a set of HED meteorites, taken from the RELAB database and three V-type asteroids, taken from MIT-UH-IRTF Joint Campaign for NEO Reconnaissance. We used the Modified Gaussian Model to fit the spectra to a series of overlapping, modified Gaussian absorptions. The fitted individual bands are validated against established laboratory calibrations. With spectral resolution extending to the near-infrared, we are able to resolve the presence of both high-calcium pyroxene (HCP) and low-calcium pyroxene (LCP) and, thus, use the HCP/(HCP + LCP) ratios to remotely trace igneous processing on the parent asteroids. A search of this mineral provides a useful probe of differentiation. The high HCP/(HCP + LCP) ratios found require extensive differentiation of these asteroids and/or their primordial parent body. The degree of melting obtained for the eucrites, using the former ratio, is comparable with that obtained for all V-type asteroids here analyzed, suggesting a comparable geologic history.