Niobium films of 4–100 nm thickness were synthesized on a silicon substrate under ultrahigh vacuum conditions. Measurements of electrical resistance showed a high temperature of the superconducting transition Tc, in the range of 4.7–9.1 K, and extremely small transition widths ΔTc in the range of 260–11 mK. The dependences of Tc and ΔTc on the magnetic field were studied, and superconducting coherence lengths and mean free paths of the conduction electrons were determined for different thicknesses of the synthesized films. A specific effect of the magnetic field on ΔTc was found, which reveals a transition from three-dimensional to two-dimensional superconductivity at thicknesses below 10 nm. The dependences of Tc and ΔTc on the films thickness and the magnitude of the magnetic field are discussed in the framework of existing concepts of superconductivity in thin films of superconducting metals.