Three series of potassium carbonate and thiocarbonate salts were synthesized, and the corresponding C-13 isotropic solid-state NMR and the aqueous solution C-13 and H-1 NMR data were collected. The series of compounds that were studied consists of(l) the parent compounds, i.e., potassium carbonate, K2CO3, potassium hydrogen carbonate, KHCO3, potassium monothiocarbonate, K2CO2S, potassium dithiocarbonate, K2COS2, and potassium trithiocarbonate, K2CS3, (2) the oxygen monoalkyl substituted derivatives of the parent compounds (OR series), i.e., three potassium O-alkylcarbonates, KO2COR, three potassium O-alkylmonothiocarbonates, KOSCOR, and three potassium O-alkyldithiocarbonates, KS2COR, all with R = CH3, CH2CH3, CH(CH3)(2), and (3) the sulfur monoalkyl substituted derivatives of the parent compounds (SR series), i.e., two potassium S-alkylmonothiocarbonates, KO2CSR; two potassium S-alkyldithiocarbonates, KOSCSR, and two potassium S-alkyltrithiocarbonates, KS2CSR, all with R = CH3 or CH2CH3. The preparation and proper characterization of KOICSR and KOSCSR with R = CH3 and CH2CH3 along with new IR and X-ray powder diffraction data for several other compounds in the series are reported for the first time in this study. Solution NMR data for KO2CSR (R = CH3, CH2CH3) and KOSCSR (R = CH3) and solid-state NMR data for K2CO2S and K2COS2 could not be obtained because they are unstable under the corresponding measurement conditions. The isotropic chemical shift values of the central carbon atoms obtained from solid-state MAS (magic angle spinning) NMR experiments deviate at most by 3 ppm from the corresponding solution values. Two major trends in the C-13 chemical shift values of the central carbon atoms were found. First, if an oxygen atom in a parent compound or in an alkyl-substituted derivative is replaced by a sulfur atom, a significantly higher chemical shift value is observed. This trend is discussed in terms of the paramagnetic contribution to the chemical shielding constant. Second, the size of the alkyl group in the monoalkyl derivatives has a very small effect on the chemical shift values of the central carbon atoms. This observation is explained using the concept of varying inductive effects produced by alkyl groups. The trends observed for the C-13 and H-1 chemical shift values of the alkyl groups follow common concepts on the structure dependency of chemical shifts.