A new concept of a solid catalyst with ionic liquid layer (SCILL) as a novel method to improve the selectivity of heterogeneous catalysts is presented. The sequential hydrogenation of cyclooctadiene (COD) to cyclooctene (COE) and cyclooctane on a commercial Ni catalyst coated with the ionic liquid [BMIM] [n-C8H17OSO3] was tested as first model system. Compared to the original catalyst, the coating of the internal surface with the ionic liquid (IL) strongly enhances the maximum intrinsic COE yield from 40 to 70 %. This effect is already achieved for a pore filling degree of only 10 % and cannot be explained by pore diffusion, as shown by experiments with different particle sizes and theoretical considerations. The IL layer is very robust and no leaching into the organic phase was detectable.