The main purpose of this article is to extend to the case of a non-smooth ambient variety \(X\) the connection of \textit{L. Ein, R. Lazarsfeld}, and \textit{M. Mustaţă} [Compos. Math. 140, No. 5 (2004; Zbl 1060.14004)] between divisorial valuations of its function field and the geometry of the arc space. The main application is that each divisorial valuation \(v\) is characterized by its values \(v(f_i)\) on a finite number of functions \(f_i\). It is pointed out that the \(f_i\) might be related with the key polynomials of \textit{S. MacLane} [Trans. Am. Math. Soc. 40, 363--395 (1936; Zbl 0015.29202)], from which a similar result can be proven. Another application is the precise characterization of monomial valuations on toric varieties in terms of a system of parameters. To every irreducible constructible subset \(C\) of the arc space of \(X\) that is not contained in the arc space of any proper subvariety, a valuation of the function field of \(X\) is attached via the order of vanishing along the generic point of \(C\). Important types of subsets of the arc space are: quasi-cylinders and contact loci. The valuations attached to irreducible components of such sets are the so-called cylinder valuations and contact valuations. The authors show that for valuations, divisorial \(\iff\) cylinder \(\iff\) contact. The proofs rely on a formula, in terms of a relative Mather canonical divisor, for the codimension of the subset of the arc space maximal among the sets defining the same divisorial valuation \(v\).
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