A vector operator is defined by the commutation relations of its components with the angular momentum operators:
$$
[L_i,A_j]=i\epsilon_{ijk} A_k \tag{1}
$$
The components $A_k$ act on kets in the regular way:
$$
A_k\vert u\rangle=\sum_{\alpha}\vert \alpha \rangle\langle \alpha \vert A_k\vert u\rangle
$$
where $\{\vert\alpha\rangle\}$ spans the HIlbert space.
What makes this a vector (or more generally a tensor operator) is that the action of components on kets is related by (1), i.e.
\begin{align}
i \langle v\vert A_z\vert u\rangle = \langle v\vert [L_x,A_y]\vert u\rangle = \langle v\vert L_xA_y\vert u\rangle - \langle v\vert A_yL_x\vert u\rangle\ ,\\
=\sum_{\alpha}\langle v\vert L_x\vert \alpha\rangle\langle \alpha \vert A_y\vert u\rangle+
\sum_{\alpha}\langle v\vert A_y\vert \alpha\rangle\langle \alpha \vert L_x\vert u\rangle \tag{2}
\end{align}
clearly showing that the matrix elements of different components are not independent but linked through matrix elements of the angular momenta.
Normally, the kets $\vert u\rangle, \vert \alpha\rangle$ and $\vert v\rangle$ will have some known angular momentum properties, v.g. $\vert u\rangle\mapsto \vert \gamma_u,\ell_u,m_u\rangle$, $\vert \alpha\rangle\mapsto \vert \gamma_\alpha \ell_\alpha m_\alpha\rangle$ and $\vert v\rangle\mapsto \vert \gamma_v \ell_v m_v\rangle$, where
$\gamma_a$ is whatever other quantum number is required to completely specify the state, so that the action of the $L_x$ (or any other component of angular momentum) can be evaluated explicitly, making the linear relation between $\langle v\vert A_z\vert u\rangle$ and
$\langle\alpha \vert A_y\vert u\rangle$ and $\langle v\vert A_y\vert \alpha\rangle$ even more explicit.