Someone ask for my availability, can I say I'm available for certain time?
I'm available for 7 o'clock
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When I say
I am available for X
X is the thing which I am available for, not the time at which I am available. One word you could use instead is "at":
I am available for X at 7 o'clock
You could even be more specific about the conditions of your availability as they relate to time:
I am available for X starting/beginning at 7 o'clock
I am available for X until/up to 7 o'clock
Can you provide some context? In what situation(s) are you stating your availability?
"For" may work if there is an appointment or something similar at 7, but then you would say it as "I'm available for the 7 o'clock." "I'm available for the 7 o'clock" may work for a shift. Otherwise, you would say (because you have said this means "can only come at") "I'm [only] available at 7 o'clock."