Mitochondrial maturation during imbibition of rice embryos follows the transition of unstructured double membrane bound pro-mitochondria to the typical cristae-rich mitochondrial structures observed in mature plant cells. During the first 48 h following imbibition, an ordered increase in the abundance of transcripts encoding mitochondrial proteins was observed. Co-incident with these changes in transcript levels was dynamic and rapid changes in mitochondrial protein content and mitochondrial function. Proteins representing components of the mitochondrial protein import apparatus are strikingly abundant in dry seeds, and a functional import apparatus was shown to operate 2 h after imbibition. Interestingly, this import process was best driven by the oxidation of NADH from outside the mitochondrial inner membrane. In later developmental stages the capacity for matrix organic acid metabolism was evident, accompanied by the appearance of proteins for TCA cycle components, and coordination of electron transport chain assembly through components encoded in both mitochondrial and nuclear genomes. Together these events provide new insights into the understanding of mitochondrial maturation and the nature of pro-mitochondrial structures in plant cells.