ESR investigations on exchange coupled pairs of Cu ions in single crystals of Cu(dtc)2, isomorphously diluted with the corresponding diamagnetic zinc salt, are reported. The spin Hamiltonian parameters for the coupled species (S=1) are:g‖=2.1025,g+=2.031,A=75.1×10−4 cm−1,B=14.8×10−4,D=276.0×10−4 cm−1 andE=46.7×10−4 cm−1. While theg andA tensors show tetragonal symmetry, the zeor-field splitting tensor is rhombic and has principal axes different from those of theg andA tensors. Intensity measurements made down to 4.2 K indicate that the exchange is ferromagnetic with |FFF| ∼ 10 cm−1. Direct dipole-dipole interaction appears to be the major contribution to the zero-field splitting. A calculation on the distributed point dipole model shows that dipolar interaction is considerably modified by the high covalency of the Cu-S bond and accounts for the rhombic nature of the tensor. The possible exchange mechanisms in Cu(dtc)2—direct exchange and superexchange through the bridging sulphurs—are discussed.