Parameter estimation of photovoltaic modules is an essential step to observe, analyze, and optimize the performance of solar power systems. An efficient optimization approach is needed to obtain the finest value of unknown parameters. Herewith, this article proposes a novel opposition-based tunicate swarm algorithm for parameter estimation. The proposed algorithm is developed based on the exploration and exploitation components of the tunicate swarm algorithm. The opposition-based learning mechanism is employed to improve the diversification of the search space to provide a precise solution. The parameters of three types of photovoltaic modules (two polycrystalline and one monocrystalline) are estimated using the proposed algorithm. The estimated parameters show good agreement with the measured data for three modules at different irradiance levels. Performance of the developed opposition-based tunicate swarm algorithm is compared with other predefined algorithms in terms of robustness, statistical, and convergence analysis. The root mean square error values are minimum (<inline-formula> <tex-math notation="LaTeX">$6.83\times 10 ^{-4}$ </tex-math></inline-formula>, <inline-formula> <tex-math notation="LaTeX">$2.06\times 10 ^{-4}$ </tex-math></inline-formula>, and <inline-formula> <tex-math notation="LaTeX">$4.48\times 10 ^{-6}$ </tex-math></inline-formula>) compared to the tunicate swarm algorithm and other predefined algorithms. Proposed algorithm decreases the function cost by 30.11%, 97.65%, and 99.80% for the SS2018 module, SolarexMSX-60 module, and Leibold solar module, respectively, as compared to the basic tunicate swarm algorithm. The statistical results and convergence speed depicts the outstanding performance of the anticipated approach. Furthermore, the Friedman ranking tests confirm the competence and reliability of the developed approach.