If the real variables $x$ and $y$ are dependent functionally on each other, say by the equations $y = f(x)$ and $x = g(y)$, then where things are differentiable, we do indeed have an equation
$$ \frac{dy}{dx} = \frac{1}{\frac{dx}{dy}} $$
and the most straightforward proof is as you indicated by the chain rule:
$$ \frac{dy}{dx} \frac{dx}{dy} = \frac{dy}{dy} = 1$$
and then solving the equation
$$ \frac{dy}{dx} \frac{dx}{dy} = 1$$
for $\frac{dy}{dx}$.
The argument can be rephrased in terms of functions rather than dependent variables: from the identity
$$ x = g(f(x)) $$
we differentiate to obtain
$$ 1 = g'(f(x)) f'(x) $$
and thus the analogous identity
$$ f'(x) = \frac{1}{g'(f(x))} $$
More generally, in the language of differential forms, the expression $\frac{dy}{dx}$ is defined to be the expression satisfying
$$ dy = \frac{dy}{dx} dx $$
if that is possible. When both $\frac{dy}{dx}$ and $\frac{dx}{dy}$ are defined, then we have two equations
$$ dy = \frac{dy}{dx} dx \qquad \qquad dx = \frac{dx}{dy} dy $$
and can substitute to obtain
$$ dy = \frac{dy}{dx} \frac{dx}{dy} dy $$
and so we again have
$$\frac{dy}{dx} = \frac{1}{\frac{dx}{dy}} $$
wherever $dy$ is nonvanishing. An example of a situation where both are defined is if the variables $x$ and $y$ are functionally related by a differentiable equation $f(x,y) = 0$. Taking the differential gives
$$ f_1(x,y) dx + f_2(x,y) dy = 0$$
where $f_1$ is the derivative of the two-variable function $f$ with respect to the first variable. When both $f_1$ and $f_2$ are nonzero, we can solve the equation in both ways to see that both $\frac{dx}{dy}$ and $\frac{dy}{dx}$ are defined.