Famous spouses Lakshmi and Parvati don't occur in Rig Veda Samhita, as far as I know.
Which Gods also have their spouses mentioned in the Rg Veda Samhita?
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A partial answer
Rig Veda 6.66.3 says that Maruts are the sons of Pṛśni.
They who are Sons of the rain-pouring Rudra, whom the long-lasting One had power to foster: The Mighty Ones whose germ great Mother Pṛśni is known to have received for man's advantage.
So Rudra and Pṛśni are couples.
Indra and Sachi are another couple mentioned in Rig Veda. ( Source yet to be mentioned)
In Rig Veda I.185.2 Heaven and Earth were mentioned as Divine parents.
bhūriṃ dve acarantī carantaṃ padvantaṃ gharbhamapadī dadhāte | nityaṃ na sūnuṃ pitrorupasthe dyāvā rakṣataṃ pṛthivī no abhvāt ||
The Twain uphold, though motionless and footless, a widespread offspring having feet and moving. Like your own son upon his parents’ bosom, protect us, Heaven and earth, from fearful danger.
Laxmi is mentioned in Rigveda.
सक्तुमिव तितउना पुनन्तो यत्र धीरा मनसा वाचमक्रत । अत्रा सखायः सख्यानि जानते भद्रैषां लक्ष्मी र्निहिताधि वाचि॥२॥
Parvati is mentioned in other Upanishads.