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My sister hates being late for work. She likes to arrive __________ time.

I know the answer is "on". What about "in"? Can we also use it in this case?

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I'd say it depends on how 'accurate' you need to be...

"on time" implies 'at the correct moment, exactly' [with some slight leeway, but not a lot]

"in time" simply implies 'at some point before I ought to be there' - it has a greater element of 'early'.

Examples...

The train arrived on time.

The train was due at 08:57, it arrived at 08:57, exactly on schedule.

I was due to be at work for 09:00, I arrived in time.

You may have arrived at 08:59, but you probably allowed some extra, so were there early, 08:50 or so.

These are not absolutes, but each version hints towards either a specific or more general time of arrival.

"in time" has an even earlier variant "in plenty of time" meaning you arrived at work well before your specified start time, maybe 08:40 - but these 'measurements' are relative to the situation & very variable.
Some people might consider being at work 2 minutes before their appointed time to be 'plenty'... others may not.
Similarly, some people might consider 'on time' to be within a few minutes either way, early or late.

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Given a choice between "on" and "in", I would agree that "on" is the better answer in this case.

"On time" usually implies that there is a specific deadline that must be met, eg the time that your sister starts work.

"In time" usually implies that some other event is going to occur, possibly not at a precise time, and the subject wants to arrive before the event occurs. For example:

We arrived at the airport in time to see her plane land.

The difference may be better understood by the following sentence.

We did not arrive on time for the start of the school concert, but we arrived in time to see Sarah's performance.

As for your sister's work habits, if she hates being late, she would be better off arriving before time instead of on time.

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