[en] We investigate the temperature dependence of the structural parameters of quasi-one-dimensional Sr_3NiRhO_6 across the region of magnetic phase transitions using Ni K-edge and Sr K-edge x-ray absorption spectroscopy (XAS). The features in the x-ray absorption near-edge region are identified using multiple scattering calculations. The temperature-dependent extended x-ray absorption fine structure (EXAFS) studies show that the setting of the intra-chain super exchange interaction starts at ∼200 K, which is well above the first transition temperature (45 K) revealed by magnetic susceptibility studies. The onset of the inter-chain super–super exchange interaction appears to be at ∼125 K. Interestingly, the role played by direct exchange interaction between the Ni 3d and Rh 4d states in stabilising the magnetic interaction is less significant. The present results shed light on the generic features exhibited by isostructural compounds and may help in identifying the magnetic exchange pathways useful for understanding the unusual properties exhibited by such compounds. (paper)