In this study, we report an Er-doped quaternary piezoelectric semiconductor CaZnOS:Er3+ which shows both mechanoluminescence and upconversion luminescence properties. Under mechanical stimulation, green light emission can be observed by the naked eye from a flexible film fabricated by encapsulating CaZnOS:Er3+ particles between two polyethylene glycol terephthalate substrates. The integral emission intensity is proportional to applied pressure, making CaZnOS:Er3+ suitable for dynamic pressure sensing applications. Moreover, the doped sample also shows bright visible emission with near-infrared (980 nm) excitation. The fluorescence intensity ratio between two upconversion emission bands corresponding to 2H11/2, 4S3/2 → 4I15/2 transitions of Er3+ is sensitive to the variation of temperature. As a multifunctional optical material, CaZnOS:Er3+ could be used to not only visualize two-dimensional pressure distribution, through mechanically induced emission, but also sense temperature via the upconversion (UC) luminescence. This work provides a novel kind of multifunctional luminescent material for the development of integrated and coupling devices.