One way the vector space $\mathbb{R}^n$ can come up is as the space of polynomials over $\mathbb{R}$ of degree at most $(n-1)$ . Here we have the isomorphism: $$(a_0,a_1,\ldots,a_{n-1}) \leftrightarrow a_0+a_1x+a_2x^2+\cdots+a_{n-1}x^{n-1}.$$ The linear independence of the polynomials in $\{1,x,x^2,\ldots,x^{n-1}\}$ is why it is legitimate to equate the coefficients of polynomials.
Question: What are other guises for the vector space $\mathbb{R}^n$?
I.e., what are some other interesting vector spaces that are isomorphic to $\mathbb{R}^n$?
As DonAntonio says in the comments, any real vector space $V$ of dimension $n$ is isomorphic to $\mathbb{R}^n$. Once you choose a basis $v_1,\dotsc,v_n$ in $V$, you can write any vector $v\in V$ uniquely as $v=\lambda_1v_1+\dotsc+\lambda_nv_n$, and so $v\mapsto(\lambda_1,\dotsc,\lambda_n)$ is an isomorphism $V\to\mathbb{R}^n$.
A subtle but important point is that the isomorphism depends on the choice of basis, so it is dangerous to say that $V$ is $\mathbb{R}^n$; you don't know how to match the elements up until you have a basis of $V$ (and a basis of $\mathbb{R}^n$, but we could take the standard one by convention). Indeed, it is even possible to define a basis of $V$ as an isomorphism $\mathbb{R}^n\stackrel{\sim}{\to}V$.
There are cases in which two objects are isomorphic via a unique preferred isomorphism (i.e. a natural isomorphism) that doesn't depend on any choices, and in that case it makes more sense to call them the same rather than just isomorphic.