Partition coefficients between olivine and melt at upper mantle conditions, 3 to 14 GPa, have been determined for 27 trace elements (Li, Be, B, Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Sr, Y, Zr, Cs, Ba, La and Ce) using secondary-ion mass-spectrometry (SIMS) and electron-probe microanalysis (EPMA). The general pattern of olivine/melt partitioning on Onuma diagrams resembles those reported previously for natural systems. This agreement strongly supports the argument that partitioning is under structural control of olivine even at high pressure. The partition coefficients for mono- and tri-valent cations show significant pressure dependence, both becoming larger with pressure, and are strongly correlated with coupled substitution into cation sites in the olivine structure. The dominant type of trace element substitution for mono- and tri-valent cations into olivine changes gradually from (Si, Mg)↔(Al, Cr) at low pressure to (Si, Mg)↔(Al, Al) and (Mg, Mg)↔(Na, Al) at high pressure. The change in substitution type results in an increase in partition coefficients of Al and Na with pressure. An inverse correlation between the partition coefficients for divalent cations and pressure has been observed, especially for Ni, Co and Fe. The order of decreasing rate of partition coefficient with pressure correlates to strength of crystal field effect of the cation. The pressure dependence of olivine/melt partitioning can be attributed to the compression of cation polyhedra induced by pressure and the compensation of electrostatic valence by cation substitution.