$\DeclareMathOperator\PSL{PSL}\newcommand\Ad{\mathrm{Ad}}\newcommand\triv{\mathrm{triv}}$I believe that if the characteristic of $k$ is 2, then $H^1(\PSL_2(k),k^3)$ is nonzero, while if the characteristic of $k$ is at least 7, then $H^1(\PSL_2(k),k^3)=0$.
I will now write $\Ad$ for the adjoint representation and $\triv$ for the trivial representation. Note that $H^1(PSL_2(k),\Ad) \cong \operatorname{Ext}^1 (\triv,\Ad)$. So we need to know if there is a non-split short exact sequence
$$0\to \Ad \to X \to \triv\to 0.$$
If $k$ has characteristic 2, then we can take the tensor square of the defining representation $X=(k^2)^{\otimes 2}$.
If $k$ has characteristic at least 7, let me sketch my solution. Start with $X$ as above. Let $N$ be the subgroup which is the normaliser of a split torus. Since $\lvert N\rvert$ is coprime to the characteristic of $k$, we can, and do, split this short exact sequence in the category of $N$-modules.
Write $e,h,f$ for the usual basis of $\Ad$ and $v$ for a basis element of $\triv$. I claim that for every $x\in k$, there exist $\alpha,\beta\in k$ such that
$$\left(\begin{smallmatrix}
1 & x \\ 0 & 1
\end{smallmatrix}\right)
\cdot v=v+\alpha e,\qquad
\left(\begin{smallmatrix}
1 & 0 \\ x & 1
\end{smallmatrix}\right)
\cdot v=v+\beta f.
$$
To prove this, I pick $t\in \mathbb{F}_p$ with $t^5\neq t$ (hence the assumption on the characteristic) and apply the identity
$$
\left(\begin{smallmatrix}
t & 0 \\ 0 & t^{-1}
\end{smallmatrix}\right)
\left(\begin{smallmatrix}
1 & x \\ 0 & 1
\end{smallmatrix}\right)
=
\left(\begin{smallmatrix}
1 & x \\ 0 & 1
\end{smallmatrix}\right)^{t^2}
\left(\begin{smallmatrix}
1 & t \\ 0 & t^{-1}
\end{smallmatrix}\right)
$$
to $v$.
Now the product $\left(\begin{smallmatrix}
1 & x \\ 0 & 1
\end{smallmatrix}\right)\left(\begin{smallmatrix}
1 & 0 \\ -x^{-1} & 1
\end{smallmatrix}\right)
\left(\begin{smallmatrix}
1 & x \\ 0 & 1
\end{smallmatrix}\right)$ lies in $N$ so must act trivially on $v$. Substituting in the equations above we end up with $\alpha=\beta=0$, which is enough to conclude as these elements generate $\PSL_2(k)$.