Enriching a biomaterial surface with specific chemical groups has previously been considered for producing surfaces that influence cell response. Silane layer deposition has previously been shown to control mesenchymal stem cell adhesion and differentiation. However, it has not been used to investigate neuronal or Schwann cell responses in vitro to date. We report on the deposition of aminosilane groups for peripheral neurons and Schwann cells studying two chain lengths: (a) 3‐aminopropyl triethoxysilane (short chain‐SC) and (b) 11‐aminoundecyltriethoxysilane (long chain‐LC) by coating glass substrates. Surfaces were characterised by water contact angle, AFM and XPS. LC–NH2 was produced reproducibly as a homogenous surface with controlled nanotopography. Primary neuron and NG108‐15 neuronal cell differentiation and primary Schwann cell responses were investigated in vitro by S100β, p75, and GFAP antigen expression. Both amine silane surface supported neuronal and Schwann cell growth; however, neuronal differentiation was greater on LC aminosilanes versus SC. Thus, we report that silane surfaces with an optimal chain length may have potential in peripheral nerve repair for the modification and improvement of nerve guidance devices.