I asked him if I might see his watch?
So can I write this above sentence like this?
I asked him that could I see his watch?
What if I use "that" instead of if?
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No, you can't use 'that' instead of 'if', because this is a reported question of the yes/no type using Indirect speech, and the form 'ask' + 'if / whether' + clause must be used. For example,
He asked me if I spoke English.
He asked me whether I was British or American.
So, if you're looking for an alternative to 'if', I suggest you use 'whether', adding an 'or not' after 'watch' (as 'whether' is used when there are two options), but 'that' is not correct.
Here are more examples for this.
Hope this helps.