Local anesthetic monohydrochlorides of [2-(alkoxy)phenyl]-2-(1-piperidinyl)ethyl esters of carbamic acid (CnA, n = 2, 3, 4, 6, 8, 10, 12 is the number of carbon atoms in the alkyloxy substituent) increase the probability of formation of gauche isomers p(g) and decrease the effective energy difference between gauche and trans conformation E(g) in egg yolk phosphatidylcholine (EYPC) acyl chains, as determined by electron spin resonance spectroscopy using dipalmitoylphosphatidylcholines labeled with the paramagnetic dimethyloxazolidinyl group on the 12-th or 16-th carbon atoms of their sn-2 acyl chain, and oriented EYPC bilayers hydrated at 81% relative water vapour pressure. CnAs also increase the hydration of EYPC in non-oriented bilayers at the same relative water vapour pressure. At the molar ratio of CnA:EYPC = 0.4:1, the maximum effect on p(g), E(g) and hydration has been observed for intermediate alkyloxy chain lengths n approximately 4/6.