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This paper proposes the use of a class of feedforward artificial neural networks with polynomial activation functions (distinct for each hidden unit) for practical modeling of high-order Volterra systems. Discrete-time Volterra models (DVMs) are often used in the study of nonlinear physical and physiological systems using stimulus-response data. However, their practical use has been hindered by computational limitations that confine them to low-order nonlinearities (i.e., only estimation of low-order kernels is practically feasible). Since three-layer perceptrons (TLPs) can be used to represent input-output nonlinear mappings of arbitrary order, this paper explores the basic relations between DVMs and TLPs with tapped-delay inputs in the context of nonlinear system modeling. A variant of TLP with polynomial activation functions-termed “separable Volterra networks” (SVNs)-is found particularly useful in deriving explicit relations with DVM and in obtaining practicable models of highly nonlinear systems from stimulus-response data. The conditions under which the two approaches yield equivalent representations of the input-output relation are explored, and the feasibility of DVM estimation via equivalent SVN training using backpropagation is demonstrated by computer-simulated examples and compared with results from the Laguerre expansion technique (LET). The use of SVN models allows practicable modeling of high-order nonlinear systems, thus removing the main practical limitation of the DVM approach