We have studied quenched high pressure phases in the CaSiO3 system by x-ray diffraction (XRD) and Si-29 MAS NMR. XRD study of the previously reported "epsilon-CaSiO3 phase" synthesized at 12 GPa and 1500-degrees-C reveals that it is actually a mixture of beta-Ca2SiO4 (larnite) and a previously unknown CaSi2O5 phase. This result is supported by the Si-29 NMR spectra. Furthermore, both the XRD and the NMR data suggest that the CaSi2O5 phase may have a titanite (CaTiSiO5) structure in which Ti is replaced by an octahedral Si. Samples quenched from 15 GPa and 1500-degrees-C consist mostly of an amorphous phase, but a small amount of CaSiO3-perovskite was identified by both XRD and NMR. The Si-29 NMR spectrum of the amorphous phase suggests that its local structure is similar to that of a glass quenched from melt at 1 bar.