She spoke with him sitting on a bench.
I think it is likely to mean she is sitting on the bench or he is sitting on the bench.
So, I wonder if there is a way to eliminate this ambiguity.
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Yes, there is ambiguity here—we cannot tell whether it was he or she who sat on the bench, or even both of them. Syntactically the likeliest predicand for sitting on a bench is him, since such modifiers typically follow their predicands immediately; but as InitK points out, the phrase may act as a secondary predicate modifying the subject, or it may act as a clausal adjunct modifying the entire clause.
No, there is no way of resolving this ambiguity in the sentence itself, though it may be resolved in context.
I think, it's not possible to say who and maybe it's not important in this case. I would still guess though and say it is she who is sitting, because she is the subject of this sentence:
She - spoke - sitting
If it would be he who was sitting it would have to be less ambiguous.
I would say at first glance most native speakers would probably assume both are sitting on the bench conversing since this is a natural and ordinary occurrence, and it is only after the ambiguity is flagged that positioning of the two participants becomes questionable.
I think the next assumption would be the man is sitting and the woman is not.
I think much less so would a listener assume the woman and not the man was sitting.
1) She spoke with him sitting on a bench.
2) She spoke with him while sitting on a bench
is also ambiguous, but more natural sounding
While sitting on a bench, she spoke with him
Sitting on a bench, she spoke with him
rearranging the exact same words in #1 and #2, may sound less ambiguous, but still remains unresolved. If anything, there is an emphasis of she being seated due to proximity to sitting
They spoke ( with each other ) while sitting on a bench
She spoke to him while they both sat on a bench
The only way to resolve this sentence would be to change the wording