Unique combination of ionic conductivity and anisotropic physical properties in ionic liquid crystals leads to new dynamic properties exploited in modern technological applications. Structural and dynamics information at atomic level for molecules and ions in mesophases can be obtained by nuclear magnetic resonance (NMR) spectroscopy through the measurements of dipole–dipole spin couplings. While ¹³C– ¹H and ¹⁵N– ¹H dipolar NMR spectra can be routinely acquired in samples with natural isotopic abundance, recording ¹⁵N– ¹³C dipolar NMR spectra is challenging because of the unfavourable combination of two rare isotopes. In the present study, an approach to measure ¹⁵N– ¹³C dipole-dipole NMR spectra in static liquid crystalline samples with natural abundance is introduced. We demonstrate that well-resolved spectra can be recorded within 10 h of experimental time using a conventional NMR probe and a moderately strong magnetic field. The technique is applied to a thermotropic smectic mesophase formed by an ionic liquid with imidazolium-based organic cation.