The L'Agent diffusion line will feature 15 styles, including bras, briefs and corsets.
Penelope said of the range: "It is so exciting for me and Mónica to embark in this new adventure. We have always been huge fans of Agent Provocateur and both of us are very much looking forward to this long term collaboration. We feel extremely happy to become part of this great team."
Monica, who is the face of the luxury underwear brand's autumn/winter 2012-13 ad campaign, demonstrated an enthusiasm for design, leading to the collaboration, reports the Vogue website.
The collection was created under the supervision of Agent Provocateur's creative director, Sarah Shotton, who said: "Mónica Cruz was sensational [in our campaign], and Penelope Cruz has always been a muse for Agent Provocateur.
"Penelope and Mónica are both long-time lingerie fans and have brought a new design sensibility to the brand. Working with the Cruz sisters was a great opportunity to bring the diffusion line to life and to further strengthen the brand's relationship with them."
The Cruz sisters have been heavily involved with all aspects of the collaboration, from the design of the labels to sourcing fabric swatches for inspiration.
The collection will be released worldwide in August 2013. It's thought that the L'Agent line will be slightly more accessible than the Agent Provocateur mainline, designed for a younger audience and carrying lower price tags.