I want to show that $\tilde{H_n}(\vee_{\alpha}X_{\alpha}) = \oplus \tilde{H_n}(X_{\alpha})$.
Note that $\tilde{H_n}(\vee_{\alpha}X_{\alpha}) = H_n(\vee_{\alpha}X_{\alpha}, x_0)$ where $x_0$ is the basepoint. Hatcher hinted that we should consider $H_n(\sqcup X_{\alpha}, \sqcup x_\alpha)$, where $x_\alpha$ is the basepoint. It seems that he is using that they form a good pair. However it does not seem to be necessarily true. Even if it is true, how does the claim follow from it?
You seem to be referring to Hatcher's Corollary 2.25. In the book, he explicitly states that it is assumed that each $(X_\alpha, x_\alpha)$ is a good pair.
As for the claim itself, the steps are: \begin{align} \widetilde H_n (\vee_\alpha X_\alpha ) & \cong H_n (\vee_\alpha X_\alpha, x_0 ) \\ &\cong H_n (\sqcup_\alpha X_\alpha / \sqcup_\alpha x_\alpha, \ \sqcup_\alpha x_\alpha / \sqcup_\alpha x_\alpha ) \\ &\cong H_n (\sqcup_\alpha X_\alpha, \sqcup_\alpha x_\alpha) \\ &\cong \oplus_\alpha H_n (X_\alpha, x_\alpha) \\ &\cong \oplus_\alpha\widetilde H_n (X_\alpha)\end{align}
To spell it out: