Here we present results on synthesis of double K-Ca carbonates at atmospheric pressure in closed graphite capsules. The mixtures of K2CO3 and CaCO3 corresponding to stoichiometry of K2Ca(CO3)2 and K2Ca2(CO3)3 were used as starting materials. The low-temperature modification of K2Ca(CO3)2 was synthesized by a solid-state reaction at 500°C during 96 h. The high-temperature modification of K2Ca(CO3)2 as well as the K2Ca2(CO3)3 compound were synthesized both by a solid-state reaction at 600°C during 72 h and during cooling of the melt from 830 to 650°C for 30 min. The obtained carbonates were studied by Raman spectroscopy. The Raman spectrum of bütschliite is characterized by the presence of an intense band at 1093 cm-1 and several bands at 1402, 883, 826, 640, 694, 225, 167 and 68 сm-1. The Raman spectrum of fairchildite has characteristic intense bands at 1077 and 1063 cm-1, and several bands at 1760, 1739, 719, 704, 167, 100 сm-1. In the Raman spectrum of K2Ca2(СO3)3 intense bands at 1078 and 1076 cm-1 and several bands at 1765, 1763, 1487, 1470, 1455, 1435, 1402, 711, 705, 234, 221, 167, 125 and 101 сm-1 were found. The collected Raman spectra can be used to identify carbonate phases entrapped as microinclusions in phenocrysts and xenoliths from kimberlites and other alkaline rocks.