(This is a rewrite of dustin's answer for my own reference.)
Clearly $f(z)=\frac{1}{e^z - 1}$ has a pole at $z=0$. Since $\lim_{z\to0}zf(z)=1$, the pole is simple. Thus $f(z)$ has a Laurent series expansion $\sum_{n\ge-1}a_nz^n$ about zero with $a_{-1}=1$. Now, as both
$$g(z)=\frac{z}{e^z - 1}=\sum_{n\ge0}a_{n-1}z^n$$
and
$$\frac{1}{g(z)}=\frac{e^z - 1}{z}=\sum_{n\ge0}\frac{z^n}{(n+1)!}$$
are analytic at zero, we have
$$\left(\sum_{n\ge0}a_{n-1}z^n\right)\left(\sum_{n\ge0}\frac{z^n}{(n+1)!}\right)=1.$$
By comparing coefficients on both sides, we see that $a_0=-\frac12$ and $\{a_n\}_{n\ge-1}$ is given by the recurrence relation $a_{-1}=1$ and
$$\sum_{k=0}^n\frac{a_{k-1}}{(n-k+1)!}=0\quad(n\ge1).$$
In particular, $a_0=-\frac12$. Finally, in a deleted neighbourhood of zero, it is straightforward to verify that
$$\sum_{n\ge1}a_nz^n=f(z)-\frac{a_{-1}}{z}-a_0
=\frac{1}{e^z-1}-\frac{1}{z}+\frac{1}{2}$$
is an odd function. Therefore, all positive even terms $a_2,a_4,\ldots$ are actually equal to zero and the previous recurrence relation can be rewritten as $a_{-1}=1,\ a_0=-\frac12$ and
$$\frac{1}{(2n+1)!}-\frac{1}{2(2n)!}+\sum_{k=1}^n\frac{a_{2k-1}}{(2n-2k+1)!}=0\quad(n\ge1).$$
Remark. The coefficients $B_n$ of the Taylor expansion
$$\frac{z}{e^z-1}=\sum_{n\ge0}\frac{B_nz^n}{n!}$$
are known as Bernoulli numbers. Thus $a_n=\frac{B_{n+1}}{(n+1)!}$ for every $n\ge-1$.