Tocochromanols (tocopherols and tocotrienols) unitedly known as vitamin E, are the necessary antioxidant components of both human and animal diets. There is a considerable interest in plants with increased or customized vitamin E content, due to their potential health benefits. To quantify the tocochromanol content and determine the expression of a key tocotrienol biosynthesis gene among a set of contrasting red pericarp and light brown rice genotypes of advanced breeding lines together with their parents; expression pattern of homogentisate geranylgeranyl transferase (HGGT), the key gene was studied by semi-quantitative RT-PCR in milky and matured grain stages. Vitamin E analysis was carried out by high performance liquid chromatography (HPLC). The chloroform-methanolic extracts prepared from red pericarp and light brown rice advanced breeding lines showed significant differences for vitamin E content. Averaged across all samples, the content of γ-tocotrienol > α-tocopherol > α-tocotrienol > γ-tocopherol > δ-tocotrienol, and total E vitamin content ranged from 10.30 to 31.65 µg/g. Genotype G37 (red pericarp) was found to have higher expression than G7 (light brown) and G33 (red pericarp) at both grain development stages but lower than both parents whereas their transcript levels were comparatively lower in mature grain, which indicates their possible regulation by plant growth stage. HPLC results of γ-tocotrienol content supported gene expression results with the exception of the recurrent parent MR219.