Yes, in fact in this situation you have more, all the Lie algebras $(V, L(t))$ (which I denote by $\mathfrak{g}_t$ to abbreviate) are isomorphic:
Let $G$ be the simply connected Lie group integrating a finite dimensional real Lie algebra $\mathfrak{g}$. Let $W$ be a finite dimensional representation of $G$, and write $W$ also for the induced Lie algebra representation of $\mathfrak{g}$.
Then the differentiable Lie group cohomology of $G$ with values in $W$ vanishes in positive degrees (this can be proven by averaging cocycles with respect to a bi-invariant Haar measure to obtain primitives for them).
The group $G$ is 2-connected (connected and simply connected by assumption, and $\pi_2(G)=0$ holds for any Lie group by a result of Hopf - see edit comment at the bottom), and so there is an isomorphism induced by the so-called Van est map in degrees up to 2, between differentiable Lie group and Lie algebra cohomology with values in $W$:
$$VE: H^k_\mathrm{diff}(G,W)\stackrel{\cong}{\to} H^k(\mathfrak{g},W),\ \ \ k=0,1,2$$
In particular, considering $W$ to be the adjoint representation of a Lie algebra on itself, one conclusion is that, in the setting of the question, $H^2(\mathfrak{g}_t, \mathfrak{g}_t)=0$.
A result of Nijenhuis-Richardson says that any Lie algebra $\mathfrak{g}$ such that $H^2(\mathfrak{g}, \mathfrak{g})=0$ is rigid, i.e., nearby Lie algebras to $\mathfrak{g}$ are isomorphic to it, where nearby is with respect to the topology you have on $S$. One possible place to read about this is the following survey:
M. Crainic, F. Schätz and I. Struchiner, A survey on stability and rigidity results for Lie algebras, Indagationes Mathematicae, 25(2014), 957-976. Theorem 5.3 there is the rigidity result.
Since every $\mathfrak{g_t}$ is rigid and the path is continuous, they will end up being isomorphic, and so $G_t$ are also isomorphic Lie groups.
Edit: the result of Hopf I had in mind only guarantees finite $\pi_2(G)$. But the result that $\pi_2(G)=0$ is true, actual proofs and references for the result are in this Mathoverflow question: Homotopy groups of Lie groups
I think I was wrong about attributing it to Hopf, what I had in mind his result only implies finite $\pi_2$, as explained in this answer: https://mathoverflow.net/a/8996/104042 .
I don't know who first proved it. Some of the references there are "Representations of compact Lie groups" by Bröcker and tom Dieck and Milnor's book on Morse theory.
– João Nuno Mestre Apr 27 '23 at 19:08There is a cohomology (Yamaguti cohomology) for Lie triple systems (Lts) that when using the Lts itself as the module (analogous to the adjoint for Lie algebras) controls the deformations of the Lts. Kubo, Taniguchi, A controlling cohomology of the deformation theory of Lie triple systems
If $H^3$ vanishes, then the Lts is rigid in some sense, see theorem 2 in that paper.
– João Nuno Mestre Apr 27 '23 at 19:42I don't know if, by analogy, this could some times be implied by some assumptions on symmetric spaces, be it compactness or some sort of connectedness (perhaps 3-connectedness in this case?).
– João Nuno Mestre Apr 27 '23 at 19:46