Carbon-13 nuclear magnetic resonance is a very useful spectroscopic technique in studying organic compounds, especially when the proton NMR does not provide much information. In this study of multicyclic lactams, different NMR techniques were used: broadband decoupled spectra, single-frequency off-resonance decoupling (SFORD), and the attached proton test (APT). Lanthanide shift reagents and lanthanide relaxation reagents were also used. Almost all the carbon-13 resonances of mono-, bi-, and polycyclolactams were unambiguously assigned. The most powerful method in the assignments was based on the use of the lanthanide induced shifts (LIS) which confirmed the assignments qualitatively and quantitatively. The quantitative confirmation comes from the calculations of LIS and their comparison with the observed shifts. The carbon-13 chemical shielding of the studied lactams was analyzed and compared with analogous compounds. The results presented provide a consistent picture and the major influences in the trends of the ¹³C chemical shifts. However, no empirical relationships were derived for this series of compounds. The solution conformations of most of these lactams have been investigated using the shifts induced in their carbon-13 NMR by Yb(dpm)₃. These conformations were compared with structures obtained from X-ray data and MINDO/3 calculations. The structural analyses of ε-caprolactam and 3-azabicyclo[4.3.1]decan-4-one showed that these molecules have at least two conformations in solution. The LIS structural analyses were confirmed by using ¹³C T₁ relaxation times in Gd(dpm)₃ and Gd(fod)₃ relaxation reagents. The different contributions to the ¹³C NMR lanthanide induced shifts (LIS) were studied with emphasis in determining the importance of the ligand pseudocontact contribution. This was found to be important, especially in carbons in proximity to the complexation site.