New intercalation compounds CrxZrSe2 were synthesized and thoroughly studied. Cr atoms were found to occupy the positions both tetrahedrally and octahedrally coordinated by the Se atoms in the interlayer gap. The magnetic properties and electrical resistivity were studied in the temperature ranges of 2.4–300 K and 80–340 K, respectively. The compounds change their behavior from semiconducting (x = 0.1) to metallic (x > 0.1). The magnetic interaction strongly depends on the Cr content and temperature. The spin-glass state with antiferromagnetic interaction exists at T < Tcrit for CrxZrSe2 with x ≤ 0.2, while at x ≥ 0.3 ferromagnetic contribution arises as well. The single crystals of CrxZrSe2 were grown to study the electronic structure of the materials. A combination of the X-ray photoelectron spectroscopy (including that across Cr 2p-3d and Zr 3p-4d resonance) and X-ray absorption spectroscopy methods allowed to propose the location of the Cr 3d-states in the Se 3p–Zr 4d energy gap.