Bismuth (Bi), as a stable heaviest element in the periodic table of elements, has strong spin-orbit coupling, which has attracted a lot of attention as the parent material of various known topological insulators. Previous calculations predicted that Bi(111) with a thickness less than eight bilayers and the ultrathin black-phosphorus-like Bi(110) films are single-element two-dimensional (2D) topological insulators. However, it is generally believed that these crystalline bismuth phases are not superconducting or their transition temperature should be lower than 0.5 mK. Lead (Pb) is a good superconducting elementary material, and there is a relatively small difference in radius between the Bi atom and Pb atom. According to the Hume-Rothery rule, it is expected that Pb/Bi alloys in an arbitrary ratio should be superconducting. One may thus expect to form crystalline Bi based superconductors by Pb substitution, which might host intriguing topological superconductivity. While our previous work has demonstrated a low-temperature stable Pb_1–xBi_x (x~0.1) alloy phase in which Pb in the Pb(111) structure is partially replaced by Bi, the Bi crystalline structure-based phases of the superconducting alloys still lack in-depth research. Here, we report a new low-temperature phase of Pb-Bi alloy thin film, namely PbBi₃, on the Si(111)-(7 × 7) substrate, by co-depositing Pb and Bi at a low temperature of about 100 K followed by an annealing treatment of 200 K for 2 h. Using low-temperature scanning tunneling microscopy and spectroscopy (STM/STS), we characterize in situ the surface structure and superconducting properties of the Pb-Bi alloy film with a nominal thickness of about 4.8 nm. Two spatially separated phases with quasi-tetragonal structure are observed in the surface of the Pb-Bi alloy film, which can be identified as the pure Bi(110) phase and the PbBi₃ phase, respectively, based on their distinct atomic structures, step heights and STS spectra. The PbBi₃ film has a base structure similar to Bi(110), where about 25% of the Bi atoms are replaced by Pb, and the surface shows a \sqrt 2 \times \sqrt 2 R45^ \circ reconstructed structure. The superconducting behavior of the PbBi₃ phase is characterized using variable-temperature STS spectra. We obtain that the superconducting transition temperature of PbBi₃ is about 6.13 K, and the 2\varDelta (0)/k_\textBT_\textc ratio is about 4.62 using the fitting parameter of \varDelta (0) = 1.22\text meV at 0 K. By measuring the magnetic field dependent superconducting coherence length, the critical field is estimated at larger than 0.92 T. We further investigate the superconducting proximity effect in the normal metal-superconductor (N-S) heterojunction consisting of the non-superconducting Bi(110) domain and the superconducting PbBi₃ domain. The N-S heterojunctions with both in-plane configuration and step-like configuration are measured, which suggest that the atomic connection and the area of the quasi-2D Josephson junctions and the external magnetic field can affect the lateral superconducting penetration length. We also observe the zero-bias conductance peaks (ZBCPs) in the superconducting gap of the PbBi₃ surface in some cases at zero magnetic field. By measuring dI/dV spectra at various temperatures and by adopting a superconducting Nb tip, we identify that the ZBCP originates from the superconductor-insulator-superconductor (S-I-S) junction formed between a superconducting tip and the sample. Nevertheless, the Bi(110)-based PbBi₃ phase may provide a possible platform to explore the intriguing topological superconducting behaviors at the vortexes under magnetic fields, or in the vicinity of the potentially topological superconducting Bi(110) islands by considering the proximity effect.