Given that \( \overrightarrow{a} = \alpha \hat{i} + \beta \hat{j} \) and \( \overrightarrow{b} = \alpha \hat{i} - \beta \hat{j} \) are perpendicular, their dot product should be zero:
\[
\overrightarrow{a} \cdot \overrightarrow{b} = 0.
\]
Calculating the dot product:
\[
(\alpha \hat{i} + \beta \hat{j}) \cdot (\alpha \hat{i} - \beta \hat{j}) = \alpha^2 - \beta^2 = 0.
\]
Thus, we have:
\[
\alpha^2 = \beta^2.
\]
This implies that:
\[
\alpha = \pm \beta.
\]
Since \( \alpha \neq \beta \), we conclude that:
\[
\alpha = -\beta.
\]
Therefore, \( \alpha + \beta = 0 \).
Thus, the correct answer is option (E).