A numerical study was carried out to investigate charging and discharging processes of different phase change materials (PCMs) used for thermal storage in an innovative solar collector, targeting domestic hot water (DHW) requirements. The aim was to study PCMs that meet all application requirements, considering their thermal performance in terms of stored and retrieved energy, outlet temperatures, and water flow rate. Work was carried out for three flat-plate solar panels of different sizes. For each panel, a PCM tank with a heat exchanger was attached on the back plate. Simulations were conducted on a 2D domain using the enthalpy−porosity technique. Three paraffin-based PCMs were studied, two (A53, P53) with phase-change temperatures of approximately 53 °C and one of approximately 58 °C (A58H). Results showed that, during charging, A58H can store the most energy and A53 the least (12.30 kWh and 10.54 kWh, respectively, for the biggest unit). However, the biggest unit, A58H, takes the most time to be fully charged, i.e., 6.43 h for the fastest feed rate, while the A53 unit charges the fastest, at 4.25 h. The behavior of P53 lies in between A53 and A58H, considering stored energy and charging time. During discharging, all PCMs could provide an adequate DHW amount, even in the worst case, that is, a small unit with a high hot water consumption rate. The A58H unit provides hot water above 40 °C for 10 min, P53 for 11 min, and A53 for 12 min. The DHW production duration increased if a bigger unit was used or if the consumption rate was lower.