Is there any rule of thumb of where and when to pronounce O (in Ukrainian words) as /a/ and when to pronounce it as /o/?

Is it supposed to be like in Russian language?

In Ukrainian you simply pronounce о as /ɔ/ and а as /ɑ/ (they are almost never intermixed).

It's true that in unstressed position vowels can be pronounced less clear than in stressed position. The most prominent example is е /ɛ/ and и /ɪ/, which both can approach [e] (so, when recovering written form from the oral form, you sometimes are unsure whether you should write е or и in unstressed position). Other vowels also may somewhat "deviate" when in unstressed position (e.g. а /ɑ/ → [ɐ], о /ɔ/ → [o], у /u/ → [ʊ]). But а /ɑ/ and о /ɔ/ "deviate" much less than in Russian, from a practical point of view you can think that а /ɑ/ and о /ɔ/ don't "deviate" at all.

Some English soruces:

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    I would lile to add, that o is mostly can be like u, but not a in those cases. Especially when we speak about West and North Ukrainian. – follower Nov 29 at 12:27
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    The sound of “о”, when followed by stressed “у”, can also deviate somewhat towards /u/ in words like “кожу́х”. Still, a learner would do well pronouncing everything as written. – Roman Odaisky Nov 30 at 1:33

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