This paper focuses on the preparation of two types of hydrophobic nanolayers using electrospinning technology. The first synthetic approach consists in direct fiberizing of polymeric phenyl-methyl-polyphosphazene Ph-Me(p) with the aim to preparing nanolayers that have significant hydrophobicity and thermal stability. The preparation of Ph-Me(p) is a multi-step reaction which produces a relatively low amount of the product. The second area of our interest was the creation of nanofibers formed from a mixture of some commercially available organic polymers and a cyclo-phosphazene derivative. In this case, tri(phenyl)-trimethyl-cyclo-triphosphazene, Ph-Me(t), whose synthesis is less complicated than its polymeric form, was used as an additive. The influence of the Ph-Me(t) additive in the nanofibers on the affinity to water was compared with the affinity of nanolayers made from a pure commercial polymer, i.e. without any phosphazene additive. It was also shown that the hydrophobic properties of fibers formed from Ph-Me(p) dissolved especially in THF are better than those of the nano fibers composed of a commercial polymer with the addition of Ph-Me(t). (C) 2016 Elsevier B.V. All rights reserved.