Maize is considered a promising candidate for biofortification through breeding, given its widespread cultivation and significance as a food crop. This cost-effective and sustainable approach could be used to increase the content of different tocol compounds, i.e., vitamin E, in maize grain due to the well-documented genetic variability. In the present study, an evaluation of the content of nine different tocol traits was performed in a genebank collection of 88 inbred lines of temperate maize grown at two locations in Croatia in 2019. A large genotypic variability within the studied material was observed for α-tocopherol, γ-tocopherol, δ-tocopherol, total tocopherols, α-/γ-tocopherol ratio, α-tocotrienol, γ-tocotrienol, total tocotrienols and total tocols with corresponding coefficients of variation of 52, 61, 51, 45, 106, 24, 54, 33 and 38%, respectively. Heritability estimates ranged from 0.66 for α-tocotrienol to 0.95 for δ-tocopherol. The content of α-tocopherol, which has the highest vitamin E activity and is therefore most interesting for selection, was not significantly correlated with either grain color or grain type. Comparison of the effects of simulated selection with an intensity of 20% on increased α-tocopherol content using the two selection criteria, absolute α-tocopherol content and α-/γ-tocopherol ratio, showed that the highest absolute α-tocopherol content was a better selection criterion. Indeed, simulated selection based on the absolute α-tocopherol content resulted in a 64% increase in this compound without significantly affecting the total tocopherols, the total tocotrienols, and the α-/γ-tocopherol ratio.