Yes, you can get pregnant any time you have sex.
Typically ovulation occurs two weeks before menstruation, and a woman is fertile for up to a week before ovulation thanks to the presence of fertile cervical mucus that can keep sperm alive in the vagina for up to a week.
Unless a woman uses Fertility Awareness Methods there is no way for her to know when she is fertile or ovulating - because everyone's cycle are different and your individual cycles can change for a number of reasons.
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