Porphyrins have attracted considerable attention as an important family of photosensitizers used for dye-sensitized solar cells (DSSCs). In this work, a novel triphenylamine-porphyrin-pyrimidine triad with a triple bond linkage was synthesized and characterized. The sensitizer presents broad absorption in solution and on TiO2 films across the UV-Vis region benefiting from the extended conjugation. The acetenyl π-conjugated bridge stimulates the photoinduced electron transfer (PET) process and brings a charge-separated state lifetime of around 4 μs. DSSC devices based on the sensitizer achieve a power conversion efficiency (PCE) of 3.77% thanks to the prolonged charge-separated state lifetime and suppressed charge recombination. The understanding of the structural, optical, and electrochemical properties of triphenylamine-porphyrin-pyrimidine triads provides new insights into the rational design of porphyrin sensitizers for various applications.