No, each woman only has about a 20% chance of getting pregnant every month. Some people may get pregnant the first time they have sex because it happened at the exact right time and luck, others will try to have a baby for 2 years with no luck.
No, you have to have sex when you're ovulating to get pregnant. Keep in mind though sperm can live inside a woman 5-7 days so if you ovulate pretty quick after your cycle, you could get pregnant.