Abstract: In order to deepen the understand of actinyl compounds’ electronic characteristics and structure-to-spectra relationships, and provide valid candidates for theoretical simulations, two types of uranyl perchlorate crystals (UO₂L₂·2ClO₄, L=N,N,N',N'-tetramethyl-diglycolamide, shortened to TMDGA) were successfully prepared by controlling different growth conditions, designated as U-1 and U-2, corresponding to low and high symmetry, respectively. Crystal structure analysis demonstrates that U-2 crystallizes in the tetragonal system with space group I4/mcm, and its structure is remarkably consistent with previously reported NpO₂L₂·ClO₄ and PuO₂L₂·2ClO₄ crystals. The highly symmetric \mathrmU\mathrmO_2\mathrmL_2^2+ unit in U-2 exhibits strikingly distinct structural and spectroscopic characteristics compared to most uranyl complexes. A unique, orderly arranged “anion channel” of \mathrmC\mathrml\mathrmO_4^- ions is distributed around the \mathrmU\mathrmO_2\mathrmL_2^2+ unit. Bond length measurements show that the U=O bond length in the low-symmetry U-1 crystal is 1.743 Å. In the high-symmetry U-2 crystal, it is 1.741 Å. Correspondingly, the symmetric stretching vibration (ν₁) of the uranyl group in U-1 is located at 863 cm⁻¹. In contrast, this vibration significantly increases to 874 cm⁻¹ in U-2. A negative correlation between U=O bond length and bond strength (indicated by vibrational frequency) is clearly revealed. The symmetric stretching vibration of the \mathrmC\mathrml\mathrmO_4^- anion in both crystals was precisely observed at 931 cm⁻¹. No difference is found compared to its Raman shift in aqueous solution. In U-1, the intensity ratio of the uranyl symmetric stretch to the \mathrmC\mathrml\mathrmO_4^- symmetric stretch is measured to be approximately 1∶2. This ratio closely resembles that observed in aqueous uranyl perchlorate solutions. However, in U-2, the relative intensity of the uranyl vibration is significantly enhanced, and its intensity ratio relative to the \mathrmC\mathrml\mathrmO_4^- vibration becomes approximately 1∶1. This indicates that crystal symmetry profoundly affects the intensity of the uranyl Raman vibration. Theoretical calculations were performed to mimic the Raman spectrum of U-2 under gas-phase conditions. The obtained results are highly consistent with the experimental spectrum, and this consistency strongly confirms the existence of the approximately vacuum-like environment created by the anion channel. Moreover, it validates the reliability of the computational methods and structural models employed in this work. These findings demonstrate the profound influence of molecular symmetry on the electronic structure and structure-spectra relationships of actinyl compounds. Furthermore, the research conclusions in this paper can provide key guidance for the establishment of accurate theoretical simulation methods for actinyl compounds.