The local spin configurations of Fe atoms in the magnetically ordered alloys Rh1−xFex (x=0.1, 0.2, and 0.3) have been investigated by Mossbauer spectroscopy. The Mossbauer absorption spectra are measured in the range from 5 K to temperatures of the transition to the paramagnetic state. The measurements in magnetic fields with a strength up to 5 T are carried out at a temperature of 4.2 K. Analysis of the magnetic-hyperfinefield distribution functions demonstrates that Fe atoms form discrete sets of collinear spin configurations corresponding to different net moments of the nearest coordination sphere. The spin structure of the alloys is governed by a random distribution of Fe atoms over the lattice sites and the competition between the Fe-Rh ferromagnetic exchange interaction and the antiferromagnetic interaction of the neighboring Fe atoms. No spin frustration and spin “melting” effects characteristic of spin glasses are revealed in the Rh-Fe alloys.