SnSe nanomaterials are challenging to use in sustainable energy production due to difficulties in phase-pure synthesis and efficient charge-carrier separation. We demonstrate a systematic facile synthesis method with an in-depth nucleation and growth mechanism for the rational design of phase-pure and morphology-controlled SnSe-based efficient and cost-effective photocatalysts. Transient absorption spectroscopy measurements are performed to investigate the charge-carrier kinetics of SnSe microflowers (MFs), which exhibit a free charge-carrier lifetime of 6.2 ps. Although the bare SnSe, CdSe, and ZnSe photoanodes demonstrate sizable photocurrents, the construction of CdSe/SnSe and ZnSe/SnSe heterojunctions dramatically improves the photoelectrochemical devices activity. The CdSe/SnSe photoanode shows higher photocurrents of 35 μA cm −2 , compared to the ZnSe/SnSe (15 μA cm −2 ) heterojunction and the individual SnSe (10 μA cm −2 ), CdSe (7 μA cm −2 ), and ZnSe (1 μA cm −2 ). The decent photoactivity of the CdSe/SnSe photoanode is attributed to the desired type-II band alignment and very small band offset (0.08 eV) that exists across the interface, which promotes the efficient separation of photogenerated electron−hole pairs confirmed by cyclic voltammetry measurements and is corroborated by firstprinciples density functional theory calculations. These findings should open new avenues for the design and development of advanced next-generation tin selenide-based heterostructures for efficient PEC water-splitting applications.