Keratinocyte carcinomas (KC) are cancers of the skin predominantly caused by ultraviolet radiation (UVR). Oral nicotinamide (Vitamin B3; NAM) is reported to reduce KC and pre-malignant lesions in healthy volunteers. Here, we report the efficacy of three monotherapies (NAM, phloroglucinol [PG], and metformin [Met]) and two combinational treatments (NAM-PG and NAM-Met) in preventing UVR-induced skin cancer. Female hairless C3.Cg-Hrhr/TifBom Tac mice were exposed to UVR of 3.5 standard erythema doses three times a week to induce skin cancer development. In three subsequent experiments, mice (n = 25 per group) were treated concurrently to UVR with i) 600 mg/kg NAM or 100 mg/kg PG, ii) 600 mg/kg NAM or 300 mg/kg Met, iii) 600 mg/kg NAM, 75 mg/kg PG + 400 mg/kg NAM, or 200 mg/kg Met + 400 mg/kg NAM. In all three experiments, a UVR control group was also included. Our data showed significant protection provided by PG and NAM monotherapies compared to the UVR control group (p ≤ 0.036). Met monotherapy did not reduce tumour development (p > 0.05). In the combination study, all three treatments protected against tumour development (p ≤ 0.015). NAM-Met was less effective compared to NAM-monotherapy (p ≤ 0.01), indicating inferior photoprotection. In contrast, NAM-PG reduced pyrimidine-pyrimidone (6-4) photoproducts measured by immunohistochemistry in comparison to both the UVR control group (40%; p ≤ 0.0021) and NAM-monotherapy (37%; p ≤ 0.0082). Our data indicate that the combination of two treatments (NAM and PG) provides effective pre-clinical photoprotection even at a reduced dose. The reduction in DNA damage could suggest that NAM and PG may synergise to mediate an improved protective mechanism better suited for keratinocyte carcinoma prevention.