Let \(n\ge 2\) and \(\Omega \) be a bounded Lipschitz domain of \(\mathbb {R}^n\) . Assume that \(L_R\) is a second-order divergence form elliptic operator having real-valued, bounded, symmetric, and measurable coefficients on \(L^2(\Omega )\) with the Robin boundary condition. In this article, via first obtaining the Hölder estimate of the heat kernels of \(L_R\) , the authors establish a new atomic characterization of the Hardy space \(H^p_{L_R}(\Omega )\) associated with \(L_R\) . Using this, the authors further show that, for any given \(p\in (\frac{n}{n+\delta _0},1]\) , \(\begin{aligned} H^p_z(\Omega )+L^\infty (\Omega )=H^p_{L_N}(\Omega )=H^p_{L_R}(\Omega )\subsetneqq H^p_{L_D}(\Omega )=H^p_r(\Omega ), \end{aligned}\) where \(H^p_{L_D}(\Omega )\) and \(H^p_{L_N}(\Omega )\) denote the Hardy spaces on \(\Omega \) associated with the corresponding elliptic operators respectively having the Dirichlet and the Neumann boundary conditions, \(H^p_z(\Omega )\) and \(H^p_r(\Omega )\) respectively denote the “supported type” and the “restricted type” Hardy spaces on \(\Omega \) , and \(\delta _0\in (0,1]\) is the critical index depending on the operators \(L_D\) , \(L_N\) , and \(L_R\) . The authors then obtain the boundedness of the Riesz transform \(\nabla L_R^{-1/2}\) on the Lebesgue space \(L^{p}(\Omega )\) when \(p\in (1,\infty )\) [if \(p>2\) , some extra assumptions are needed] and its boundedness from \(H_{L_R}^{p}(\Omega )\) to \(L^{p}(\Omega )\) when \(p\in (0,1]\) or to \(H^{p}_r(\Omega )\) when \(p\in (\frac{n}{n+1},1]\) . As applications, the authors further obtain the global regularity estimates, in \(L^{p}(\Omega )\) when \(p\in (0,p_0)\) and in \(H^{p}_r(\Omega )\) when \(p\in (\frac{n}{n+1},1]\) , for the inhomogeneous Robin problem of \(L_R\) on \(\Omega \) , where \(p_0\in (2,\infty )\) is a constant depending only on n, \(\Omega \) , and the operator \(L_R\) . The main novelties of these results are that the range \((0,p_0)\) of p for the global regularity estimates in the scale of \(L^p(\Omega )\) is sharp and that, in some sense, the space \(X{:}{=}H^1_{L_R}(\Omega )\) is also optimal to guarantee both the boundedness of \(\nabla L^{-1/2}_R\) from X to \(L^1(\Omega )\) or to \(H^1_r(\Omega )\) and the global regularity estimate \(\Vert \nabla u\Vert _{L^{\frac{n}{n-1}} (\Omega ;\,\mathbb {R}^n)}\le C\Vert f\Vert _{X}\) for inhomogeneous Robin problems with C being a positive constant independent of both u and f.