The local structural response to magnetic ordering in polycrystalline Cr0.3Fe0.7VO4 has been examined using synchrotron x-ray diffraction, x-ray absorption fine structure, and Raman spectroscopy. The combined structural analyses indicate that the average M-O (M = Cr/Fe) and V-O coordination environments remain essentially unchanged across the magnetic transition TN≃21 K, implying that nearest-neighbor bond distortions do not play a role in driving the magnetic ordering. Instead, subtle modifications occur at TN in the intercluster M-O-V linkages, consistent with tilting and/or rotation of MO6 octahedra and VO4 tetrahedra. EXAFS analysis further identifies a tendency toward preferential occupation of the more distorted M1 sites by Cr3+ and the more regular M2 sites by Fe3+, which shapes the mixed d3–d3, d3–d5, and d5–d5 exchange interactions in the M4O16 clusters. We propose that five competing superexchange pathways within each cluster give rise to intrinsic intracluster frustration and short-range ordering, which propagates through M-O-V-O-M linkages to modulate geometric frustration at larger length scales. Raman measurements reveal only weak spin-phonon coupling confined to a narrow temperature region of 15-25 K, tentatively attributed to this frustration. These results suggest a hierarchical frustration scenario in which the local cation distribution shapes the exchange network, whereas the subtle inter-polyhedral distortions represent a structural response coupled to the evolving magnetic correlations. These interpretations are inferred from structural and macroscopic magnetic data and direct validation by neutron diffraction, µSR, or density functional theory (DFT) calculations is needed.