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Combining the molecular dynamics (MD) simulations and the free-energy-based thermodynamic analysis, we analyze the role of alkyl chain length on the nucleation of alcohol molecules with the mono-hydroxyl in nanoconfined solution. The free energy formulae and thermodynamic equilibrium equation are parameterized by fitting the theoretical equilibrium equation to MD simulation results. We find that alcohol molecules with the varied alkyl chain length show different nucleation states, i.e. , dispersion, reversible and aggregation states, corresponding to the total free energy G c o n f i n e (n , N) with a single minimum at n ∼ 1, two minima at n ∼ 1 and N separated by a maximum, and a local minimum at n ∼ N , respectively. The alcohol molecule with a longer alkyl chain tends to aggregate into a cluster at a lower solute number in nanoconfined solution. Besides, the free energy of cluster formation in nanoconfined solution G c l u s t e r (n) also depends on the alkyl chain length, and three regions can be identified: For the shorter alkyl chain, such as ethanol, there is no local maximum on G c l u s t e r (n), indicating that alcohol molecules tend to be dispersed in water; For the intermediate alkyl chain length, such as 1-propanol, 1-butanol, 1-pentanol, and 1-hexanol, the critical nucleation number n c and nucleation barrier G b monotonically decrease with the increase of alkyl chain length; For the longer alkyl chain, n c ∼ 1 and G b ∼ 0 k B T suggest that alcohol molecules, such as 1-heptanol, can aggregate into clusters easily. Our work deepens the understanding of the alkyl chain length effect on the nucleation behavior of alcohol molecules in nanoconfined solution. [ABSTRACT FROM AUTHOR]