I think the answer should be this, but not sure. Can anyone help me?
{ }, {(0,0)}, {(0,1)}, {(1,0)}, {(1,1)}, {(0,0), (0,1)}, {(0,0), (1,0)},
{(0,1), (1,0)}, {(0,1), (1,1)}, {(1,0), (1,1)}, {(0,0), (0,1), (1,1)}, {(0,0), (1,0), (1,1)},
{(0,0), (0,1), (1,0), (1,1)}
Try to approach this in a systematic way. What is the possible size of a relation on a two-element set $S$? Well, it can't have more then $4$ elements, which is the relation $S\times S$. So, the possibilities are $0,1,2,3,4$. The case of $0$ elements gives just the empty relation, which is symmetric. The case of $1$ element entails looking at, e.g., $\{(0,0)\}$, which is symmetric, but also at $\{(0,1)\}$ which is not symmetric. The other two possibilities are very similar and you can probably suspect what you'll get already. Continue in this manner and you'll see the general pattern, and you'll make sure you did not miss any cases.