High resolution carbon-13, fluorine-19, and proton NMR measurements in solutions of the monosubstituted bullvalenes, C(10)H(9)X with X = F, CN, and COOH, as function of temperature are reported. The spectra at low temperatures exhibit signals due to more than one isomer (three for X = F and two for X = CN, COOH). On heating the peaks broaden due to bond shift (Cope) rearrangement involving the various isomers. Detailed analysis of the line shapes shows that in all cases interconversion between the four possible isomers must be assumed, even though the concentration of some of them is too weak to be observed. For fluorobullvalene a complete analysis of the interconversion kinetics and equilibria is presented. For cyanobullvalene and bullvalenecarboxylic acid only a semiquantitative analysis of the results was made.