You create a new key/value pair on a dictionary by assigning a value to that key

d = {'key': 'value'}
print(d)  # {'key': 'value'}

d['mynewkey'] = 'mynewvalue'

print(d)  # {'key': 'value', 'mynewkey': 'mynewvalue'}

If the key doesn’t exist, it’s added and points to that value. If it exists, the current value it points to is overwritten.