This paper investigates the asymptotic properties of least squares estimates of Hammerstein-Wiener model structures, and in doing so establishes consistency and asymptotic normality under fairly mild conditions on the additive noise process, the inputs and the static nonlinearities. In relation to the asymptotic distributional results, a consistent procedure for the estimation of the asymptotic variance of the parameter estimates is provided. A key theme of this paper is to demonstrate how recent results from the econometrics literature may be employed in an engineering setting. In this respect the Hammerstein-Wiener model structure serves as a demonstration example. A simulation study complements the theoretical findings.