Tunnel magnetoresistance (TMR) of diamondoids has been predicted by first principles density functional theory. Diamantane was used as a basic molecular proxy for diamondoids because hydrogen atoms in the apical position are easily substituted for a thiol group. The pristine diamantane exhibited a low TMR ratio of 7%, and boron-substitution considerably decreased the TMR ratio. Conversely, nitrogen-substitution enhanced the TMR ratio by up to 20%. Heteroatom-substitution changes the tunneling probabilities by varying the molecular bond lengths. Furthermore, when the spins of the electrodes are parallel, the heteroatoms resulted in transmittance probabilities at an energy range near the Fermi level. Consequently, heteroatom-substitution can control the TMR ratios of diamondoids very well. (C) 2016 Elsevier B.V. All rights reserved.