Using density functional theory (DFT) with the B3LYP, PBE, and PBE0 exchange-correlation functionals as well as the Møller-Plesset second-order perturbation theory (MP2) combined with a series of rather extended basis sets, H1 and C13 chemical shifts of small alkanes and chloroalkanes (with different numbers of chlorine atoms on specific positions) have been simulated and compared to experimental data. For the H1 chemical shifts, theory tends to reproduce experiment within the limits of the experimental errors. In the case of C13 chemical shift, the differences between theory and experiment increase monotonically with the number of chlorine atoms and exhibit a deviation from additivity. This behavior is related to the saturation of the experimental C13 chemical shifts with the number of chlorine atoms, whereas the evolution is mostly linear at both DFT and MP2 levels of approximation. This difference has been traced back to the relativistic spin-orbit coupling effects, which are exalted as a result of the enhancement of the s character of the C atom when increasing the number of linked Cl atoms. Thus, it was demonstrated that not only electron correlation but also relativistic effects have to be considered for estimating the C13 chemical shifts when several Cl atoms are directly attached to the C atom. Linear (theory/experiment) regressions have then been performed for the different types of C atoms, i.e., bearing one, two, and three Cl atoms, with excellent correlation coefficients. The linear correlation relationships so obtained can then serve to predict and facilitate the interpretation of the nuclear magnetic resonance spectra of more complex compounds. Furthermore, by investigating the basis set effects, the correlation between the chemical shifts calculated using the 6-311+G (2d,p) basis set and the more extended 6-311+G (2df,p) and aug-cc-pvtz basis sets is excellent, demonstrating that the choice of the 6-311+G (2d,p) basis set for calculating the H1 and C13 chemical shifts is relevant.