A model of catalytically enhanced CVD growth of a silicon nanowire assembly on a substrate is developed, and growth process is simulated. Thermodynamickinetic theory is used for modeling of molecular transport in the gas phase, processes near catalyst surface and nanowire side of variable curvature, bulk diffusion of silicon adatoms through catalyst-body, and 2D nucleation. The simulation of atomic transport across surfaces is based on a long-wave approach of lattice gas approximation. To determine a character of atomic transport in TiSi 2-catalyst that is of great importance for application in Si-based technology, a density functional theory is used. The main result of modeling is that it is found a relationship between growth conditions (an initial radius of catalyst particles, their density, substrate temperature, content, pressure of gas, as well as properties of materials used) and, on the other hand, a growth rate, shape, composition, and type of atomic structure (amorphous or crystalline) of the nanowires grown. Besides, available experimental data published previously are discussed, and a qualitative agreement between theory and various experiments is obtained. This agreement gives rise to use the found relationship for controlling the nanowire growth.