We study the electronic structure of GdCrTiO5 polycrystals by means of magnetic susceptibility and heat capacity measurements, as well as x-ray absorption spectroscopies on the Cr 2p, Ti 2p and O 1s levels. The experimental results were interpreted with Charge Transfer Multiplet and Density Functional Theory calculations. Magnetic susceptibility and specific heat measurements indicate a long-range antiferromagnetic ordering at 0.9 K probably related to the Gd sublattice. The results indicate that spin-orbit interaction, rather than hybridization, may be crucial for the stabilization of magnetic ordering in the RCrTiO5 (R = rare earth) family.