The qualitative and quantitative quality of DFT methods combined with different basis sets in computing the J-coupling of the types 1J(C–F) and nJ(F–F) are investigated for the fluorobenzene and fluoropyridine derivatives. Interestingly, all of the computational methods perfectly reproduced the experimental order for nJ(F–F) but many failed to reproduce the experimental order for 1J(C–F) coupling. The functional PBEPBE gives the best quantitative values that are closer to the experimental spin–spin coupling when combined with the basis sets aug-cc-pVDZ and DGDZVP but is also part of the methods that fail to perfectly reproduce the experimental order for the 1J(C–F) coupling. The basis set DGDZVP combined with all the methods except with PBEPBE perfectly reproduces the 1J(C–F) experimental order. All the methods reproduce either the positive or the negative sign of the experimental spin–spin coupling except for the basis set 6-31+G(d,p) which fails to reproduce the experimental positive value of 3J(F–F) regardless of what type of DFT methods was used. The values of the FC term is far higher than all other Ramsey terms in the one bond 1J(C–F) coupling but in the two, three and four bonds nJ(F–F) the values of PSO and SD are higher.