To contribute to better understanding of the structure–property relationship for chiral liquid crystalline materials a series of new liquid crystalline (LC) materials possessing several (S)-lactate groups as chiral centres have been designed and investigated. All the materials possess the orthogonal paraelectric smectic A* phase stable over a broad temperature range. For the specific lengths of the chiral and non-chiral alkyl chains the ferroelectric tilted smectic C* phase have been detected at lower temperatures. The mesomorphic behaviour and structural properties of new multilactate materials have been studied by polarizing optical microscopy, differential scanning calorimetry, small angle X-ray diffraction and dielectric spectroscopy. The obtained results are discussed and compared to that of the structurally similar lactic acid derivatives. The main objective of the present work is to establish the molecular structure – mesomorphic property relationship for this specific class of multilactate-based LC materials, which can be further successfully utilized as chiral dopants for the design of smart multicomponent LC mixtures targeted for application in optoelectronics and photonics.