Chromium (Cr)-coated zirconium alloy cladding has emerged as one of the leading accident-tolerant fuel (ATF) solutions in recent years. This study aims to evaluate the impact of the Cr coating on the cladding’s heat transfer performance by conducting an experimental investigation into the surface pool boiling heat transfer performance of Cr-coated zirconium alloy cladding and zirconium alloy cladding under atmospheric pressure. Bubble dynamics parameters, pool boiling heat transfer curves, and critical heat flux (CHF) for both cladding types were obtained. The experimental data were compared and analyzed to assess the surface heat transfer performance of both cladding types. The main conclusions are as follows: (1) The pool boiling heat transfer process on the surfaces of both cladding types was divided into four sections based on observed bubble images: natural convection, isolated bubble nucleate boiling, slug bubble nucleate boiling, and film bubble nucleate boiling. (2) In the isolated bubble nucleate boiling section, the Cr-coated zirconium alloy cladding exhibited a higher bubble departure frequency compared to the zirconium alloy cladding; in the slug bubble nucleate boiling section, the Cr-coated zirconium alloy cladding generated more bubbles with more intense bubble interactions, enhancing heat transfer on its surface. (3) The CHF value of the Cr-coated zirconium alloy cladding increased by approximately 9% compared to the zirconium alloy cladding. (4) A heat transfer model based on the mechanisms of microfilm layer evaporation and vapor–liquid exchange was developed. The model established in this paper showed good agreement with the experimental data when the surface heat flux of the cladding was greater than 100 kW/m2. The predicted surface heat flux for the Cr-coated zirconium alloy cladding was within ±15%, and for the zirconium alloy cladding, it was within +10% and −15%.