Conventional photoacoustic endoscopy (PAE) is mostly for structural imaging, and its molecular imaging ability is quite limited. In this work, we address this issue and present the development of a flexible acoustic-resolution-based photoacoustic endoscopic (AR-PAE) probe with an outer diameter of 8 mm. This probe is driven by a micro-step motor at the distal end, enabling flexible and precise angular step control to synchronize with the optical parametric oscillator (OPO) lasers. This probe retains the high spatial resolution, high penetration depth, and spectroscopic imaging ability of conventional AR-PAE. Moreover, it is capable for background-free high-specific photoacoustic molecular imaging with a novel pump-probe detection technique, as demonstrated by the distribution visualizing of the FDA approved contrast agent methylene blue (MB) in an ex-vivo pig ileum. This proposed method represents an important technical advancement in multimodal PAE, and can potentially make considerable contributions across various biomedical fields.