Renewable energy deployment and implementation of a circular economy will play a crucial role in decreasing CO2 emissions to meet the target from the Paris agreement. Dye-sensitized solar cells (DSSCs) can be designed in various colors and transparency for building-integrated photovoltaics (BIPV). This emerging technology has gained significant attention for its remarkably high power conversion efficiency (PCE) under indoor lighting up to 34%. To improve the performance of DSSCs, various approaches to study and reduce the interfacial electron recombination from the conduction band of the semiconductor to the electrolyte were implemented in this thesis. One of the approaches was the design of a tandem electrolyte containing two redox species, the radical AZADO (AZ+/0) and the [Co(bpy)3]2+/3+ complex. DSSCs with tandem electrolytes showed increased open-circuit voltage (VOC) up to 1009 mV and enhanced PCE of 9.15%. The VOC enhancement was determined to result from the higher redox potential of (AZ+/0) and the slower electron recombination rate. These findings demonstrate the advantages of employing tandem electrolytes to improve the VOC and overall performance of DSSCs. To decrease the solvent's volatility and the interfacial electron recombination in cobalt-based electrolytes, hyperbranched networks (HB) were designed through a click thiol-ene reaction between a thiol-siloxane and an acrylate monomer. The formed polymers were denoted HB1 (thiol-siloxane and PEGMA) and HB2 (thiol-siloxane and PEGMA). The addition of 20% of HB polymers to a cobalt-based electrolyte retained up to 98% of their initial weight until 150°C. The devices employing 10%(v/v) of HB1 attained the highest PCE under AM1.5 of 8.52%, comparable to 9.36% for the cobalt reference electrolyte. All the HB-electrolytes presented higher VOC values than the cobalt reference due to an upward shift in the CB of TiO2 and longer electron lifetimes. It was determined that the HB-polymers reduce the electron recombination and enhance the photovoltaic performance under low light intensity leading to a PCE of 23.19% under 1000 lux compared to 20.37% for the Co-reference. We then developed a new dye, R7, with a strong electron-donating PAH core and BPT2 as the central building block and a bulkier HF donor to decrease electron recombination at the interface TiO2/electrolyte. We found that in the presence of a copper electrolyte, the dye R7 outperformed devices with R6. EIS revealed that the bulky HF-donor introduction effectively suppressed the electron recombination between the TiO2 surface and the redox shuttle. Additionally, we employed a co-sensitized system of R7+Y123 to reach the outstanding parameters of JSC of 16.15 mAcm-2, VOC of 1035 mV, FF of 0.76 to achieve a top PCE of 12.7%. To the best of our knowledge, this is the highest for copper-based DSSCs using a blue photosensitizer. Lastly, the interfacial phenomena in DSSCs with carbon counter electrodes (CCEs) and copper-based electrolytes were studied to determine the feasibility of the production of monolithic DSSCs with copper-based hole-transporting materials. It was found that the electron transport in devices with CCEs is in the same order of magnitude as those with PEDOT. However, the devices with CCEs presented a decrease of 2 orders of magnitude in the recombination resistance, resulting in decreased VOC and JSC, leading to a PCE of 17% compared to 24.5% for PEDOT devices under 1000 lux illumination.