Hexacyanoferrate(II) (HCF4–) and related polycyanometallates have long been recognized as multiple electron donors. Their rigid octahedral geometry and ability to participate in extensive hydrogen bonding make them excellent platforms for assembling supramolecular multidimensional charge-transfer complexes (CTCs) with various organic electron acceptors. Among these, pyridinium oximes are intriguing due to their dual role as electron acceptors and hydrogen bond donors/acceptors. Recent studies showed that supramolecular association of pyridinium oximes and HCF4– resulted in formation of CTCs with intricate stimuli-responsive optical properties revealed as reversible redox-active[1] or redox-inert[2] hydrochromic behavior. Despite their promising role in building functionalized materials, an understanding of how structural modifications within pyridinium oxime moiety affect the properties of self-assembled CTCs is still limited. The present study addresses this gap by a comparative solid-state structural and spectroscopic study of novel HCF4–-based pyridinium-oxime CTCs. Variations in the number and position of an oxime group on the pyridinium ring allowed us to elucidate the intricate relationship between their structural features and structural and optical properties of their HCF4–-based charge-transfer complexes.