A nematic liquid crystalline network based on a poly(propylene imine) dendrimer [PPI-(NH2)(32) (G = 4)] was prepared in the form of films. In the network the PPI dendritic molecules are partially functionalised with a chiral aldehyde and are connected to each other by an achiral dialdehyde. The phase behaviour of the network was investigated by polarising-light optical microscopy, differential scanning calorimetry, and X-ray diffractometry. Thermoelastic measurements ruled out the possible elastomeric nature of the material.