The atomic structure of the Si–O–C tetrahedral network of an amorphous silicon oxycarbide polymer-derived ceramic (PDC) of the composition SiO0.94±0.11C1.13±0.08 was studied at both the short range and the intermediate range using 1D and 2D 29Si nuclear magnetic resonance (NMR) spectroscopic techniques, respectively . The 1D 29Si magic angle-spinning NMR spectrum of the PDC indicates that the Si–O–C network consists of SiO4, SiO3C, SiO2C2, and SiC4 units with relative abundances of approximately 26, 25, 20, and 29%, respectively. The 2D 29Si extended CSA amplification spectrum of this PDC shows that the chemical shift anisotropy (Δ) of the mixed-bond SiOxC4–x units is significantly higher than that of the SiO4 units. On the other hand, the unusually high Δ-value for the SiC4 units was interpreted to be indicative of its role as the connecting element between the Si–O–C network and the free-carbon nanodomains. The 2D 29Si double-quantum correlation NMR spectrum of this PDC indicates that there is extensive direct linking between SiO4 and SiO3C units in the Si–O–C network besides the connectivity between like SiOxC4–x units, while the SiO4 and SiO2C2 units are only linked via a SiO3C unit. In contrast, the SiO3C units show no restriction in linking with the other SiOxC4–x units in the network. Finally, the SiC4 units show significant clustering, which is consistent with their spatial localization at the interface between the Si–O–C network and the sp2 C nanodomains. Such a spatial distribution of the SiOxC4–x units is argued to be consistent with their mass-fractal dimensions measured in previous studies.