Solution:

Let $a, b, c \ge 1$ count the $\$20, \$50, \$100$ bills. Then $20a + 50b + 100c = 800,$ which divides down to $2a + 5b + 10c = 80.$ Both $2a$ and $10c$ are even, so $5b$ is too, forcing $b = 2t.$ Now $a = 40 - 5t - 5c \ge 1$ means $t + c \le 7.$ With $t, c \ge 1,$ the pairs number $1 + 2 + \cdots + 6 = 21.$ Thus, B is the correct answer.