Before we even consider $P(Y < 3X)$, note that we have the condition $0<x<y$. Because this specifies both the upper and lower bounds for $x$, the natural way to write the the integral over the support of $f_{X,Y}$ is:
$$ P(\Omega) = \int_0^\infty \int_0^{\color{red}y} 2 e^{-x} e^{-y} dx \, dy $$
You can confirm for yourself as a preliminary exercise that this equals 1. Note that the inner integral is over $x$ with $y$ appearing as bound; therefore it will be convenient if we first solve the inequality for $x$:
$$ \begin{align}
y & < 3x & \\[0.7em]
3x & > y & \\[0.7em]
x & > y/3
\end{align} $$
We can use this to restrict the inner integral by adjusting the lower bound of the inner interval. The upper bound of $y$ is retained from above, the lower bound of $y/3$ is new and comes from the inequality which defines our event.
$$ \begin{align}
P(Y < 3X) & = \int_0^\infty \int_{\color{red}{\tfrac{y}{3}}}^{\color{red}y} 2 e^{-x} e^{-y} dx \, dy \\[1em]
& = \int_0^\infty \Bigg( -2 e^{-x} e^{-y} \Bigg|_{\tfrac{y}{3}}^{y} \Bigg) dy \\[1em]
& = \int_0^\infty (-2e^{-y}e^{-y}) - (-2e^{-y/3}e^{-y}) dy \\[1em]
& = \int_0^\infty -2e^{-2y} + 2 e^{-4y/3} dy \\[1em]
& = \frac{-2 e^{-2y}}{-2} + \frac{ 2 e^{-4y/3} }{-4/3} \Bigg|_0^\infty \\[1em]
& = e^{-2y} - \frac{3}{2} e^{-4y/3} \Bigg|_0^\infty \\[1em]
& = (0 - 0) - (1 - \frac{3}{2}) \\[1em]
& = \frac{1}{2} & \square
\end{align}
$$