A ducted photovoltaic façade (DPV) unit was studied using experimental prototype and simulated in a full scale computational fluid dynamics (CFD) model. The study comes in two parts; this is Part I, as detailed in the title above, and Part II is titled “A Ducted Photovoltaic Façade Unit with Buoyancy Cooling: Part II CFD Simulation”. The process adopted in the experimental study is replicated in the simulation part. The aim was to optimize the duct width behind the solar cells to allow for a maximum buoyancy-driven cooling for the cells during operation. Duct widths from 5 to 50 cm were tested in a prototype. A duct width of 45 cm had the maximum calculated heat removed from the duct; however, the lowest cell-operating temperature was reported for duct width of 50 cm. It was found that ΔT between ducts’ inlets and outlets range from 5.47 °C to 12.32 °C for duct widths of 5–50 cm, respectively. The ducted system enhanced module efficiency by 12.69% by reducing photovoltaic (PV) temperature by 27 °C from 100 °C to 73 °C. The maximum measured heat recovered from the ducted PV system was 422 W. This is 48.98% from the incident radiation in the test. The total sum of heat recovered and power enhanced by the ducted system was 61.67%.