Recently, oriented external electric fields (OEEFs) have earned much attention due to the possibility of tuning the properties of electronic systems. From a theoretical perspective, one can resort to electronic structure calculations to understand how the direction and strength of OEEFs affect the properties of electronic systems. However, for multi-reference (MR) systems, calculations employing the popular Kohn-Sham density functional theory with the traditional semilocal and hybrid exchange-correlation energy functionals can yield erroneous results. Owing to its decent compromise between accuracy and efficiency for MR systems at the nanoscale (i.e., MR nanosystems), in this study, thermally-assisted-occupation density functional theory (TAO-DFT) is adopted to explore the electronic properties of n-acenes (n = 2--10), containing n linearly fused benzene rings, in OEEFs, where the OEEFs of various electric field strengths are applied along the long axes of n-acenes. According to our TAO-DFT calculations, the ground states of n-acenes in OEEFs are singlets for all the cases examined. The effect of OEEFs is shown to be significant on the vertical ionization potentials and vertical electron affinities of ground-state n-acenes with odd-number fused benzene rings. Moreover, the MR character of ground-state n-acenes in OEEFs increases with the increase of the acene length and/or the electric field strength.