It's because every row operation can be viewed as the product of an elementary matrix on the left and the original matrix on the right. An elementary matrix is the identity matrix with 1 row operation performed on it, for example the elementary matrix
1 0 0
0 1 0
0 5 1
represents the operation R3 <-- R3 + 5*R2
and you can verify that when you left-multiply the above matrix by any 3x3 matrix, the result is the row operation R3 <--R3 + 5*R2
So when you row reduce A to the identity matrix I, it is equivalent to left-multiplying it by a sequence of elementary matrices E1...Ek as follows:
Ek*E(k-1)*...*E3*E2*E1*A = I
So the matrix Ek*E(k-1)*...*E3*E2*E1, which is the same as Ek*E(k-1)*...*E3*E2*E1*I, is the inverse of A. But Ek*E(k-1)*...*E3*E2*E1*I is just the transformations represented by E1...Ek being applied to the identity I in the same order, which is exactly the procedure to find the inverse.