Let $(V,g)$ be an oriented Euclidian vector space of dimension $2n$, with a non-singular operator $A\in End(V)$ anti-symmetric, then $w_A(u,v)=g(u,Av)$ defines a linear symplecitc form. Define its Pfaffian by $\frac{w_A^n}{n!}=Pf(A)\mathrm{vol}$, where $\mathrm{vol}$ denotes the volume form of $V$.
You can pull back the relation $\frac{w_A^n}{n!}=Pf(A)\mathrm{vol}$ by a $B\in End(V)$. You will get
$$Pf(B^TAB)=Pf(A)\det(B). $$
Use the normal form theorem in linear symplectic geometry, we may assume $V=\mathbb{R}^{2n}$ and $(w_0,g_0,J_0)$ denotes the standard compatible triple and there's $P:(V,w_A)\to (V,w_0)$ symplectomorphism. $$w_A(u,v)=g_0(u,Av)=P^*w_0(u,v)=w_0(Pu,Pv)=g_0(J_0Pu,Pv)=g_0(P^TJ_0Pu,v)=g_0(-Au,v).$$ So, $A=P^TJ_0^{-1}P$, and $Pf(A)^2=\det(A)$.
But this proof uses the normal form theorem. Is there a more geometrical one without citing this theorem?
Here is another idea of how to prove it geometrically, but still using a basis theorem. $\newcommand{\innprod}[1]{\left\langle #1 \right\rangle}$
Perhaps you have come across this theorem, or perhaps in a slightly different form. It is not difficult to prove, I can outline the steps if you like.
But now it is simple to check that $\det A = \lambda_1^2 \cdots \lambda_n^2$, and that $$ \omega^n(e_1, \ldots, e_n, f_1, \ldots, f_n) = n! \, \lambda_1 \ldots \lambda_n \operatorname{vol}(e_1, \ldots, e_n, f_1, \ldots, f_n)$$ hence $\operatorname{Pf}(\omega) = \pm \lambda_1 \ldots \lambda_n$ and indeed we have $\operatorname{Pf}(\omega)^2 = \det(A)$.
I would count this proof as very geometric, since the actual definition of Pfaffian (of a linear operator) depends on understanding the interaction between the orthogonal structure $\innprod{-, -}$ and the induced symplectic structure $\omega(-, -)$.