Given a normal subgroup $N$ of group $G$, the quotient group $G/N$is defined by the usual group multiplication $$[a]\star [b]=[a \cdot b]$$ where $\star$ is the group multiplication in $G/N$ and $\cdot$ is the group multiplication in $G$, and $[\cdot]$ denotes the equivalence classes, or the elements of $G/N$ defined by $$[a]=\{g\in G | g\cdot a^{-1} \in N\}$$.
I want to know that if the sense that $[\cdot] : G \rightarrow G/N$ can be viewed as a homomorphism from $G$ to $G/N$ is correct.

Can't you just check this directly? Call your map $\phi: G \to G/N$. Then for any $a, b \in G$, $$ \phi(ab) = abN = aN bN = \phi(a)\phi(b). $$ Or, if you want to stick with your class-box notation, $$ \phi(ab) = [ab] = [a][b] = \phi(a)\phi(b). $$ This follows directly from how we define the operation on cosets.