We propose a novel signature with four-photon final states to probe $CP$-violating (CPV) extended Higgs sectors via $f\overline{f}\to Z^{*}\to H_1{H}_2\to 4\gamma$ processes with $H_{1,2}$ being additional neutral Higgs bosons. We focus on the nearly Higgs alignment scenario, in which the discovered Higgs boson almost corresponds to a neutral scalar state belonging to the isospin doublet field with the vacuum expectation value $v\simeq 246\mathrm{GeV}$. We show that the branching ratios of $H_{1,2}\to \gamma \gamma$ can simultaneously be sizable when CPV phases in the Higgs potential are of order one due to the enhancement of charged-Higgs boson loops. Such branching ratios can be especially significant when the fermiophobic scenario is taken into account. As a simple example, we consider the general two Higgs doublet model, and demonstrate that the cross section for the four-photon process can be 0.1 fb at LHC with the masses of $H_{1,2}$ to be a few 100 GeV in the Higgs alignment limit under the constraints from electric dipole moments (EDMs) and LHC Run-II data. We also illustrate that the searches for EDMs and diphoton resonances at high-luminosity LHC play complementary roles to explore CPV extended Higgs sectors.