Single crystals of the quaternary europium compounds EuRhAl4Si2 and EuIrAl4Si2 were synthesized by using the Al Si binary eutectic as a flux. The structure of the two quaternary compounds has been refined by single crystal X-ray diffraction. Both compounds are stoichiometric and adopt an ordered derivative of the ternary KCu4S3 structure type (tetragonal tP8, P4/mmm). The two compounds reported here represent the first example of a quaternary and truly stoichiometric 1:1:4:2 phase crystallizing with this structure type. In light of our present results, the structure of the BaMg4Si3 compound given in literature as representing a new prototype is actually isotypic with the KCu4S3 structure. Local spin density approximation including the Hubbard U parameter (LSDA + U) calculations show that Eu ions are in the divalent state, with a significant hybridization between the Eu 5d, Rh (Ir) 4d (5d), Si 3p and Al 3p states. Magnetic susceptibility measured along the [001] direction confirms the divalent nature of the Eu ions in EuRhAl4Si2 and EuIrAl4Si2, which order magnetically near similar to 11 and similar to 15 K, respectively.