Strong quantum confinement in InP is observed to significantly reduce the separation between the direct and indirect conduction band states. The effects of three-dimensional confinement are investigated by tailoring the initial separation between conduction band states using quantum dots (QDs) of different sizes and hydrostatic pressure. Analyses of the QD emission spectra show that the X 1c states are lowest in energy at pressures of ϳ6 GPa, much lower than in the bulk. The transition to the X 1c states can be explained by either a sequence of G-L and L-X crossings, or by the crossover between strongly coupled G and X states. PACS numbers: 71.24. + q, 71.55.Eq, 73.20.Dx, 78.55.Cr Quantum confinement has dramatic effects on the optical and electronic properties of semiconductors. Quantum confinement gives rise to electron states whose energy can be varied with the confinement dimensions, and dramatically changes the density of states from steplike in one-dimensionally confined quantum well systems to atomiclike in three-dimensionally confined quantum dots (QDs). The changes in the density of states and the possibility of tailoring the band gap have attracted attention for the application of quantum confined systems in the design of optoelectronic devices.In zinc blende quantum well structures, quantum confinement has also been found to alter the electronic structure. Increased carrier confinement leads to (i) an electronic configuration in which multiple quantum wells (MQWs) of direct band-gap semiconductors become intrinsically indirect, i.e., L 1c or X 1c are the lowest conduction band states in the well, or (ii) a type II conduction band alignment with the lowest indirect conduction band state located in the barrier and the highest valence band state in the well. The former case is obtained in InGaP͞InAlP MQWs and the latter is observed in GaAs͞AlAs MQWs for well widths less than 35 Å [1,2].In three-dimensionally confined systems, model calculations predict quantum confinement to significantly alter the electronic structure of zinc blende semiconductors as the lower effective mass G 1c state rises to higher energy much faster than the higher effective mass L 1c and X 1c states [3,4]. In strained III-V QDs grown epitaxially, the interplay between carrier confinement and strain could result in either a type II electronic configuration with X 1c -derived states in the capping layer and holes in G 1y -derived QD states, or in a type I configuration where the indirect states in the QD are lowest in energy [4]. Instead, in freestanding colloidal QDs, only an intrinsically indirect electronic configuration is possible [3,5]. The model calculations predict G-X transitions to be observed in freestanding GaAs QDs with diameter ,40 Å [6], and in InP QDs at pressures around 7 GPa, as confinement alone is not sufficient to lower the X-like states below G-like states even for zero dimension [3].In this Letter, we present the first experimental evidence showing that strong quantum confinement significantly reduces the se...