Complete active space multiconfiguration self-consistent-field (CASSCF) followed by multireference singles plus doubles configuration-interaction (MRSDCI) calculations which include 27 active electrons are carried out on eight low-lying electronic states of Rh3. The MRSDCI calculations included up to 2.3 million configurations. The spin-orbit effects are included by using the relativistic configuration-interaction (RCI) method. All the low-lying states considered here lie within 0.20 eV. All the doublet states are Jahn–Teller components of the doubly degenerate 2E′ and 2E″ states in equilateral triangular geometry (D3h), while the quartet states arise from the Jahn–Teller components of 4E′ and 4E″ states. The splittings between the two Jahn–Teller components of both the 2E′ and 2E″ states, which yield barriers to pseudorotation, are 3.9 kcal/mol. The lowest-lying 2A2 and 2A1 states are separated only by 0.03 eV. Thus, low-lying electronic states of Rh3 are best described using a dynamic Jahn–Teller model. The Mulliken population analyses of the MRSDCI natural orbitals reveal the larger s population of the apex atom of the isosceles triangle in comparison to the base atoms. The base atoms have larger d populations for all electronic states. The present calculations also reveal a considerable mixing among the 4d85s1, 4d9, and 4d85p1 configurations of the rhodium atom. The atomization energy of Rh3 is calculated as 188 kcal/mol. The trimer (Rh3) is predicted to be considerably more stable than the dimer (Rh2).