If $M$ is a connected compact $2$-manifold, then it unknots in $\Bbb R^5$. More generally, $k$-connected $n$-manifolds embed in $\Bbb R^{2n-k}$ and unknot in $\Bbb R^{2n-k+1}$ in the metastable range $m>\frac{3(n+1)}2$. This was proved around 1961 - by Roger Penrose, J.H.C. Whitehead, and Zeeman in the PL category; and by Haefliger in the smooth category. Later Zeeman and Irwin extended the PL result to codimension three (see Zeeman's "Seminar on Combinatorial Topology").
On the other hand, the disjoint union of two $2$-spheres is a compact $2$-manifold. It definitely knots in $\Bbb R^5$ as detected by the linking number. That is the degree $\alpha$ of $S^2\times S^2\to S^4$, $(p,q)\mapsto \frac{f(p)-g(q)}{||f(p)-g(q)||}$, calling our link $p\sqcup q:S^2\sqcup S^2\to\Bbb R^5$. A nontrivial link is the Hopf link, whose components are the factors of the join $S^5=S^2*S^2$. Since $S^2$ unknots in $\Bbb R^5$, the exterior of one component is always homotopy equivalent to $S^2$, and the linking number is also the degree $\lambda$ of $p(S^2)\to S^5\setminus q(S^2)\simeq S^2$. [In different dimensions, where $\alpha$ and $\lambda$ are not numbers but homotopy classes of spheroids (more precisely $\alpha$ factors though a spheroid up to homotopy, upon killing the wedge), their relation is more interesting: $\alpha$ equals the suspension of $\lambda$ (up to a sign).]
By Haefliger's theorem (1963) that embeddings in the metastable range are classified by equivariant homotopy of two-point configuration spaces, the linking number for each pair of components is the only invariant of smoothly embedded $2$-manifolds in $\Bbb R^5$. This recovers the result that connected surfaces unknot in $\Bbb R^5$; and additionally implies that there is nothing new for $3$-component links. [In contrast, there are the Borromean rings of three $3$-spheres in $\Bbb R^6$, whose nontriviality is detected e.g. by a nonvanishing triple Massey product in the complement. Thinking of the usual Borromean rings in $\Bbb R^3$ as lying in the three coordinate planes, one can similarly do three copies of $S^1*S^1$ lying in the two-factor subproducts of $\Bbb R^2\times\Bbb R^2\times\Bbb R^2$.]
Also smooth, PL and topological knot theories coincide for smooth $n$-manifolds in smooth $m$-manifolds in the metastable range $m>\frac{3(n+1)}2$ (this includes $2$-manifolds in $\Bbb R^5$). In more detail, Haefliger's classification theorem implies that if two smooth embeddings in the metastable range are isotopic (=homotopic through topological embeddings, possibly wild) then they are smoothly isotopic. Weber's PL classification theorem (1967) implies additionally that every PL embedding of a smooth manifold in the metastable range is ambient isotopic to a smooth embedding. Also it follows from results of Edwards and Bryant that an arbitrary topological embedding in codimension $\ge 3$ is isotopic to a PL embedding, and, from results of Bryant-Seebeck, that a locally flat topological embedding is ambient isotopic to a PL embedding.