For which classes of topological spaces Euler characteristics is defined?

The answer to the question as it is stated is that there is probably no "largest" class of spaces for which the Euler characteristic makes sense.

The answer also depends on where you would like the Euler characteristic to take values. Here is the tautological answer (admittedly not a very exciting one): if you have a category $C$ of spaces closed under taking cones and cylinders, then there is the universal Euler characteristic for that category: just take the free abelian group $K(C)$ that has a generator $[X]$ for each $X\in C$ and quotient it by the span of $[X]+[Cone(f)]-[Y]$ for all $X,Y\in C$ and any morphism $f:X\to Y$ in $C$. The Euler characteristic of any $X$ in $C$ is set to be $[X]$. (There may be variations and/or generalizations of this approach.)

The group $K(C)$ is complicated in general but for some choices of $C$ it has interesting quotients. This can happen e.g. when $C$ admits a good "cohomology-like" functor. For example if $C$ is the category of spaces with finitely generated integral homology groups then $K(C)$ maps to $\mathbf{Z}$ and this gives the usual Euler characteristic. If one takes $C$ to be formed by spaces that admit a finite cover with finitely generated integral homology groups (typical examples are the classifying spaces of $SL_2(\mathbf{Z})$ and more generally of mapping class groups), then $K(C)$ does not map to $\mathbf{Z}$ any more, but it maps to $\mathbf{Q}$. This gives the rational Euler characteristic.

Finally, let me address the last remark by Dmitri. For some categories the group $K(C)$ maps to $\mathbf{Z}$ in several different ways. Let us take e.g. $C$ to be the category formed by spaces whose one-point compactification is a finite CW-complex (with proper maps as morphisms). Then there are (at least) two characteristics; one is obtained using the ordinary cohomology and another one comes from the Borel-Moore homology. On complex algebraic varieties both agree. But the Borel-Moore Euler characteristic of an open $n$-ball is $(-1)^n$.

Here is the answer to the second question: suppose $Y$ is a locally closed subspace of a locally compact space $X$ such that $X,Y,\bar Y,\bar Y\setminus Y, X\setminus\bar Y$ and $X\setminus Y$ are of the form "a finite CW-complex minus a point". Then $\chi(Y)+\chi(X\setminus Y)=\chi(X)$ where $\chi$ is the Euler characteristic computed using the Borel-Moore homology.

The case when $Y$ is closed follows from the Borel-Moore homology long exact sequence. In general we can write $\chi(X)=\chi(X\setminus\bar Y)+\chi(\bar Y)=\chi(X\setminus\bar Y)+\chi(\bar Y\setminus Y)+\chi(Y)$. In the last sum the sum of the first two terms gives $\chi(X\setminus Y)$ since $X\setminus\bar Y$ is open in $X\setminus Y$.

The Euler Characteristic can be defined for a larger class of spaces. For example, Euler Characteristic is defined for definable sets in an o-minimal system such as: semi-linear sets, semi-algebraic sets, algebraic varieties, compact smooth manifolds... and not all of them are locally compact.

However, when they are not locally compact, then it is not necessarily true that the different definitions of the characteristic give the same result. If you are interested in this point of view you can read:

• L. Van den Dries. Tame topology and o-minimal structures. Vol. 248. London Mathematical Society Lecture Notes Series. Cambridge University Press, 1998.

• J. Curry, R. Ghrist y M. Robinson. “Euler calculus with applications to signals and sensing”. Proceedings of Symposia in Applied Mathematics. Vol. 70. 2012, pages: 75-146. (they have a pdf freely and legally available online here)