Parity-time (PT)-symmetric Hamiltonians have widespread significance in non-Hermitian physics. A PT-symmetric Hamiltonian can exhibit distinct phases with either real or complex eigen spectrum, while the transition points in between, the so-called exceptional points, give rise to a host of critical behaviors that holds great promise for applications. For spatially periodic non-Hermitian systems, PT symmetries are commonly characterized and observed in line with the Bloch band theory, with exceptional points dwelling in the Brillouin zone. Here, in non-unitary quantum walks of single photons, we uncover a novel family of exceptional points beyond this common wisdom. These "non-Bloch exceptional points" originate from the accumulation of bulk eigenstates near boundaries, known as the non-Hermitian skin effect, and inhabit a generalized Brillouin zone. Our finding opens the avenue toward a generalized PT-symmetry framework, and reveals the intriguing interplay among PT symmetry, non-Hermitian skin effect, and non-Hermitian topology.