Hello,Tyrannosaurusss ;)
Which of these words you can use, has mainly determined by the gender of a noun.
"Он" always refers to some man ,a male animal or a masculine noun.
Some example:
a)Он всегда выглядит опрятным и ухоженным.(a man)
b)Он не кусается.(When you taking about your lovely dog,for instance)
c)Этот булыжник очень большой.Да он просто огромен!(The 'cobblestone' has masculine properties as a noun in Russian).
"Она" is just opposite and refers to woman ,a female animal or a feminine noun.
a)Она как всегда выше всяких похвал.
b)Она очень игрива.(She is very playful(a pussycat)).
When you refer to group of people (or a bunch of animals,plants etc.),regardless of their gender/sex,you can say "oни".
a)Они решили отдохнуть в конце рабочего дня.(people)
b)Они просто чудо!(flowers).
"Oно" is neuter and refers often to an inanimated object in a neuter form.
a)оно дырявое.(the bucket)
b)Дерево сохнет. Оно уже очень старое.('The tree' is a neuter noun in Russian.)