The petrology and mineralogy of shock melt veins in the L6 ordinary chondrite host of Villalbeto de la Peña, a highly shocked, L chondrite polymict breccia, have been investigated in detail using scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and electron probe microanalysis. Entrained olivine, enstatite, diopside, and plagioclase are transformed into ringwoodite, low-Ca majorite, high-Ca majorite, and an assemblage of jadeite-lingunite, respectively, in several shock melt veins and pockets. We have focused on the shock behavior of diopside in a particularly large shock melt vein (10 mm long and up to 4 mm wide) in order to provide additional insights into its high-pressure polymorphic phase transformation mechanisms. We report the first evidence of diopside undergoing shock-induced melting, and the occurrence of natural Ca-majorite formed by solid-state transformation from diopside. Magnesiowüstite has also been found as veins injected into diopside in the form of nanocrystalline grains that crystallized from a melt and also occurs interstitially between majorite-pyrope grains in the melt-vein matrix. In addition, we have observed compositional zoning in majorite-pyrope grains in the matrix of the shock-melt vein, which has not been described previously in any shocked meteorite. Collectively, all these different lines of evidence are suggestive of a major shock event with high cooling rates. The minimum peak shock conditions are difficult to constrain, because of the uncertainties in applying experimentally determined high-pressure phase equilibria to complex natural systems. However, our results suggest that conditions between 16 and 28 GPa and 2000–2200 °C were reached.