A unified framework for understanding the electronic nature of alkyl substituents is presented, resolving the contradiction between spectroscopic data and reactivity patterns typically found in organic chemistry textbooks. This framework is based on the distinct interactions of alkyl groups with σ frameworks and π systems. When attached to an sp3-hybridized atom, as in alkanes, amines, and ethers, the alkyl group acts as an inductive electron-withdrawing substituent (relative to hydrogen). This behavior reflects the greater electronegativity of carbon than hydrogen, as evidenced by NMR chemical shifts and dipole moments. The stability trends observed for aliphatic carbanions and free radicals (ethyl < isopropyl < tert-butyl in both cases) are due to this electron-withdrawing character. The acidity trend of alcohols in aqueous mixtures (methanol > ethanol > 2-propanol > tert-butanol) correlates with the decreasing permittivities of the pure alcohols. Apparent electron-donating effects inferred from Gibbs free energy acidities of ammonium ions and substituted acetic acids arise from entropic artifacts caused by hydrophobic effects. When the alkyl group is bonded to an sp2-hybridized atom, as in alkenes, arenes, carbonyl compounds, carboxylic acids, amides, heterocycles, and carbocations, or to an sp-hybridized atom, as in alkynes, concurrent hyperconjugative electron donation occurs, which overcomes the inductive electron-withdrawing effect in the tert-butyl cation. This work calls for revising textbooks to emphasize both electronic effects and to replace the misinterpreted reactivity examples with spectroscopically validated models, thereby providing a consistent framework essential for educating students and training AI systems in chemistry.

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