Taking a lead from our OP Idonknow I too checked the linked wiki page on the Pfaffian, but couldn't see how it applies to odd-sized matrices, so here's a pretty simple demonstration based on eigenvalues:
Observation: A real skew-symmetric matrix $A$ of odd size $n$ is always singular; that is, $0$ is an eigenvalue of $A$, and hence $\det A = 0$.
Proof of Observation: The characteristic polynomial of such $A$,
$\chi_A(x) = \det(A - xI) \tag{1}$
is of odd degree $n$; hence it has at least one real root $\mu$, which is an eigenvalue of $A$; thus there exists a unit vector $\vec e \in \Bbb R^n$
such that
$A \vec e = \mu \vec e; \tag{2}$
therefore,
$\mu = \mu \langle \vec e, \vec e \rangle = \langle \vec e, \mu \vec e \rangle = \langle \vec e, A \vec e \rangle = \langle A^T \vec e, \vec e \rangle = \langle -A \vec e, \vec e \rangle$
$= -\langle \mu \vec e, \vec e \rangle = -\mu \langle \vec e, \vec e \rangle = -\mu, \tag{3}$
since
$\langle \vec e, \vec e \rangle = 1; \tag{4}$
thus, since
$\mu = -\mu, \tag{5}$
we conclude that
$\mu = 0, \tag{6}$
whence
$A\vec e = 0, \tag{7}$
that is,
$\ker A \ne \{ 0 \}, \tag{8}$
$A$ is singular, and finally
$\det(A) = 0, \tag{9}$
since it is the product of the eigenvalues of $A$. End: Proof of Observation.
Note: In the above it has been proved that any real eigenvalue of a skew-symmetric matrix must be zero; however, we only need one such $\mu = 0$ to obtain the requisite result. End of Note.
So $$\det(A)=0 $$
I'm not sure how you could use the Pfaffian since it seems to be only defined for even dimensions.
– Kitegi May 18 '15 at 11:17