The term diagonalisable needs to be qualified by the field$~K$ over which one is working; for this reasons it is best to talk of diagonalisable linear operators (where $K$ is implicit in the vector space$~V$ that the operator acts upon) rather than matrices; the latter can be interpreted over various fields, and may be diagonalisable over some but not over others. The question stresses that that matrix has real entries, but that does not prevent it from being the matrix of a complex linear operator; I will however take this as an indication that being diagonalisable as a real linear operator is meant.
Given an annihilating polynomial for the linear operator, here $X^4-1$, one can always (in principle) factor it into pairwise relatively prime factors in $K[X]$, and obtain a direct sum decomposition of$~V$ into the kernels of those factors evaluated at the linear operator (or matrix). Here the finest such decomposition for $K=\Bbb R$ is $X^4-1=(X-1)(X+1)(X^2+1)$, so we get a decomposition $V=\ker(A-I)\oplus\ker(A+I)\oplus\ker(A^2+I)$. Each of these spaces might be $\{0\}$. When they are not, the first two spaces are the eigenspaces for $\lambda=1$ and $\lambda=-1$, respectively. However the third subspace does not contain any eigenvectors of$~A$, since the corresponding eigenvalue would have to satisfy $\lambda^2+1=0$ which is impossible for real values$~\lambda$. Having a nonzero dimensional $A$-stable subspace without eigenvectors ensures that $A$ is not diagonalisable (the restriction to a stable subspace of a diagonalisable operator is always diagonalisable), so one gets that $A$ satisfying $A^4=I$ is diagonalisable over$~\Bbb R$ if and only if $\ker(A^2+I)=\{0\}$. Equivalently, since this condition means that one has $V=\ker(A-I)\oplus\ker(A+I)$, it is diagonalisable if and only if $A^2=I$.
Just for completeness, such $A$ is always diagonalisable over $\Bbb C$, since the complex vector space $W$ acted upon decomposes $W=\ker(A-I)\oplus\ker(A+I)\oplus\ker(A-\mathbf iI)\oplus\ker(A+\mathbf iI)$, in which each of the summands is an eigenspace if it differs from$~\{0\}$.